CN102077060B

CN102077060B - A monitoring system based on etching of metals

Info

Publication number: CN102077060B
Application number: CN200980125930.7A
Authority: CN
Inventors: G·帕特尔
Original assignee: Individual
Current assignee: JP Laboratories Inc
Priority date: 2008-06-04
Filing date: 2009-06-04
Publication date: 2014-10-29
Anticipated expiration: 2029-06-04
Also published as: EP3293493A1; BRPI0913415B1; JP5833920B2; CN102077060A; KR20120010557A; EP3293493B1; ZA201009026B; JP2011530085A; KR101655144B1; RU2507516C2; RU2010154102A

Abstract

Compositions, devices and processes related to etching of a very thin layer or fine particles of a metal are disclosed for monitoring a variety of parameters, such as time, temperature, time-temperature, thawing, freezing, microwave, humidity, ionizing radiation, sterilization and chemicals. These devices have capabilities of producing a long and sharp induction pepod of an irreversible visual change The devices are composed of an indicator comppsing a very thin layer of a metal (e g, polyester film having an extremely thin, e g, about one hundred Angstroms layer of aluminum) and an activator, e g, a reactant, such as water, water vapor, an acid, a base, oxidizing agent or their precursors, which is capable of reacting with the said indicator. The indicator retains its opacity and metallic luster, e g, silvery white, mirror like finish of aluminum layer for a long time. The activator destroys the indicator layer including the naturally formed oxide layer.

Description

A kind of monitoring system based on corroding metal

[technical field]

The present invention relates to a kind of for monitoring time, Time-temperature, humidity, thaws, radiation, chemistry and biopreparate and sterilization based on thin metal layer or the etched system and method for particulate.The invention still further relates to pattern, printing forme, the formation of electronic circuit and RFID equipment.

[background technology]

prior art brief introduction

The shelf-life of weighing perishable farm products, conventionally adopt represent the excess time of the final use of prescribed limits.Here so-called " perishable commodities " or " perishable farm products " comprise as fresh, and refrigeration is freezing, vegetables, fruit, meat, fish, poultry, dairy produce, cake, fruit juice, the food of precooking, the perishable farm products such as soft drink and alcoholic beverage, also comprises that the non-food stuff kind having from several hours to shelf-life several years that can weigh the shelf-life comprises medicine, vaccine, serum, blood, blood plasma, cosmetics, active chemistry, biochemical product, biological products, battery, X-ray and can photographic roll film.

Whenever clock or timer become useless or use when too expensive, the color that is used in the window of sign on time marker or indicating equipment, label or tag can change.The indicator of being responsible for monitoring time passage relative populations be here known as time marker (TI) or persond eixis equipment, include but not limited to time visual confirmation, safety label, from the retail label that clocks, biological industry process monitoring, prevent reusable termination label, employee ID and safe ID label, guest id, dwelling period full scale label, parking tag, wrist strap, train, motorbus, competitive sports, theater admission ticket equal time indicating label, go sightseeing, emergency ward, hospital, no through traffic museum and other places label, be shown to airdrome control personnel on airport and see the luggage checking by specific project, wallet, chest is by the safety label checking, unattended but by visitor's entrance of video management send expire visit electronic tag.Also comprise and limit the useful products that we once open or should use over a period to come, include but not limited to beverage, food class, health, individual and residential care product.TI also can be used for monitoring the shelf-life of perishable farm products.

Time temperature indicator (TTI) equipment provides a kind of method of indicating accumulative total open-assembly time and temperature.TTI equipment can indicate temperature that whether commodity expose within a period of time than predetermined temperature larger or time and temperature round values.For example, TTI equipment can be indicated and is exposed to one or whole excess temperature in excessive time period.In patent documentation, having a lot of time temperature indicators and time marker is heat reduction and the shelf-life mark of monitoring perishable farm products, the report of label and mark.A lot of these equipment are based on from diffusion based on chemical action to another, sometimes by a permeable layer, introduce color change in indicator layer.Other TTI is based on chemical reaction, and as the diacetylene polymkeric substance of solid forms, PH can cause changing and photochromic and thermochromism can cause variation.

Existing a large amount of report for monitoring time and time-temperature round values equipment in patent documentation.

Bart's that, U.S. Patent number 5053339 discloses a kind of for monitoring the change color equipment of storage process Time-temperature, for example, the shelf-life of perishable farm products.The composition of this equipment is (1) activator band, contains activator species on substrate, and (2) indicator strip, contains indicator and substrate, (3) permselective layer.This pervious course is commonly referred to barrier layer in the prior art.In general, here this or similarly equipment be commonly referred to biobelt equipment, biobelt TTI and TI.Here, term " bonding agent ", " medium ", " ink ", " coating ", and " communication media ", " coating " and " matrix " is often replaced use.On the basis of technique, first has produced biobelt TTI/TI product the Bowater PLC company of London, has a kind of adhesive sticker form and another kind of folding product on the market during 1991 and 1993.

Haas and his colleague are at a series of U.S. Patent numbers 4903254,5053339,5446705,5602804,5633835,5699326,5715215,5719828,5785354,5822280,5862101,5873606,5930206,6446865,6452873,6752430,7139226 and 7263037 disclose time supervision equipment and related process.All these patents are included in the range of application of this patented claim.These equipment are the activator (also comprising coloring agent) based on adopting medium equally.This indicator has matrix, as has the ink of bonding agent.

It is below other representational examples of some TI and TTI equipment: U.S. Patent number: 2896568, 3018611, 3046786, 3078182, 3311084, 3520124, 3921318, 3954011, 3962920, 3999946, 4154107, 4195058, 4212153, 4382063, 4404922, 4432630, 4432656, 4448548, 4480749, 4542982, 4573711, 4629330, 4643122, 4643588, 4646066, 4737463, 4779120, 4812053, 4846095, 4846502, 4917503, 5053339, 5058088, 5120137, 5293648, 5317980, 5364132, 5378430, 5446705, 5602804, 5633836, 5667303, 5699326, 5709472, 5715215, 5719828, 5785354, 5822280, 5862101, 5873606, 5930206, 5957458, 5974003, 5997927, 6042264, 6103351, 6214623, 6254969, 6514462, 6524000, 6536370, 6614728, 6752430, 6822931, 6916116, 7156597, 7157048, 7209042, 7280441, 7290925 and 7294379.All these patents are included in the range of application of this patented claim.

The report of neither one and any one biobelt indicating equipment based on as the metal material of indicator and metal etch in bibliographical information.

While preparing edible frozen food, precook and extensively use till today.The quick-frozen food of precooking heating or be for example, with conventional oven (, using rock gas or electrical heating) or micro-wave oven more easily.Micro-wave oven can not be to food homogeneous heating.Some part of food may also not complete, and other parts may be overheated.Therefore, this just needs an indicating equipment that color can change in the time that food gives out steam.

Microwave interaction material general provision, for example, increases the area of heating surface, micro-wave screening face, the energy diffusivity of increase microwave transmission and wrappage.Receptor in micro-wave oven is microwave energy to be converted into heat while preparing for food, in order to take heating cooking food by heat conduction, convection current and/or the radiation the same with microwave.In existing document, there is the report of many microwave energy receptors.At U.S. Patent number 6501059,5530231, in 5220143,5038009,4914266,4908246,4883936,4641005 and 4267420 disclosed embodiment, receptor is included the range of application of this patented claim in.What some were similar pass through, and to select metal to be controlled at the model of conventional metals microwave absorption layer of the heat in receptor presumptive area also open.Some technology have been used to provide desirable model.U.S. Patent number 614259,5300746,5254821,5185506,4959120,4927991,4685997, the 4610755 and 4552614 open typical technologies of describing are included the range of application of this patented claim in.

Also not about the report of boiling indicating equipment as the microwave of microwave energy receptor utility appliance.

There are in the literature much reports about the indicating equipment that thaws, comprise following patent: U.S. Patent number 3233459,3702077,3786777,4038936,4114443,4120818,4144834,4163427,4280361,4735745,4892677,5267794,5685641 and 5695284.This indicating equipment when product temperature has exceeded unnecessary 0 DEG C just there is change color.These equipment can not make us being satisfied with completely because lack visual perception characteristic or its use danger, the complicacy of the sensitivity of its thaw condition or production or use.The shortcoming of this equipment is that they are failure in practice often.

The product that easily degenerates that some must refrigerate, as ice cream, frozen food, blood product and some drugs, if they are placed on to the above temperature of freezing point (normally zero degrees celsius), they can degenerate rapidly.Therefore, this just strongly need to have and thaw or melt indicating equipment.More existing reports about thawing indicating equipment in the literature.There is no a kind of thawing indicating equipment is that successful main cause is that their change color are too fast on market.When a people goes to buy vegetables, one picks up a Frozen Food Packaging, is placed on shopping cart, and payment out, is placed on automobile/shopping bag it and then goes back to be put in refrigerator.In normal process process these products that easily degenerate do not lose its quality or at short notice only because vessel surface or food the inside very fraction be more than freezing point temperature.Therefore, this change color that just need to melt indicating equipment has certain delay.In order to monitor freezing state and shelf-life or the product freezing quality that easily degenerates, this just needs " thawing-Time-temperature (TTT) indicating equipment ".This just need to be the same with the integer-valued effect of temperature with the time more than freezing point temperature in order to monitor the indicating equipment of thawing.

If a lot of commercial products bear responsive to temperature and they or even the short time be exposed near high temperature or below freezing, just may damage, degenerate or lose quality.Some fresh flowers, green salad, vegetables and herbal medicine, when being exposed to below freezing or withering while approaching freezing point temperature, atrophy and become dark color, useless and/or not attractive.Such variation is well-known, mainly causes because ice crystal has destroyed the integrality of vegetable cell.Other some freezing products that easily degenerate comprise medicine, serum, and vaccine, fresh produce, flowers, latex, coating, as milk, fruit juice and Yoghourt emulsion.Therefore, freezing indicating equipment is very important.

U.S. Patent number 3934069 discloses a kind of method for packing of salt/dye well organic carboxyl acid solution of water insoluble solvent.U.S. Patent number 3888631 discloses a kind of temperature indicating equipment of monitoring the frozen product degree of depth, is made up of fibrous material and two kinds of water-soluble colourless reagent of the similar paper that contains cementing agent.U.S. Patent number 4163427 disclose a kind of freezing-melt indicating equipment structure and comprise multiple frangible microcapsules.U.S. Patent number 5910314 discloses a kind of microcapsules preparation method of mixture.

But, not about the report of the freezing indicating equipment of known activator/etchant in freezing point and thin metal layer or metal particle etching face.

A large amount of medical supplies and the pasteurization material of other article and technology, as steam, xeothermic, oxirane, plasma, Peracetic acid, formaldehyde and energy-rich radiation.Kitchen articles, as be in and the plate used of restaurant, cutter, and cooker too need to be with hot water or the hot gas of approximately 90 DEG C be sterilized conventionally in dish-washing machine.Key is to guarantee that these article have sterilized or reached regulation requirement.More existing sterilization indicating equipments in the literature, the report of mensuration meter or detector.They comprise biological and chemical indicating equipment.Adopt low price and the widespread use of the chemical indicating equipment of change color.

A large amount of food, particularly tinned food, medicine, medical supplies need sterilization.These and other products, as sheet, by sterilizing to kill biosome to acceptable level.Direct aseptic test is passive and very expensive, thus indirectly testing mode as change color indicating equipment be available.

In hospital with high pressure steam sterilize reusable Medical Devices and articles for use, as outer cover and bedding.Also do not process with indicating equipment for distinguishing the box that the box of the goods of sterilizing is housed and the goods of also not sterilizing is housed.The process of sterilization can cause the change color of equipment.General originally color be light color and to process color be later dark.The variation of color is by ink generation chemical reaction.This indicating equipment may be strip, card-like, or belt shape.The change color of observing sterilization indicating equipment, can judge whether this package has passed through the whole series and disinfected.

International standard, as ISO (International Standards Organization) (ISO) and the involved sterilization of European standard (EN) test comprise moise-heat sterilization.

The international standard that is made up of the test of the vacuum and steam sterilizer speed of evacuation chemical indicating equipment can find in ISO and EN standard series part of detecting.These parts comprise Bowie-Dick test and the similar operation standard of seeing at AAMI (Used In The Regulation of Medical Device In Usa association), but use different testing procedures.

There are in the literature a lot of moise-heat sterilization indicating equipments and some reports for sterilization monitor.Wherein a very little part is used heavy metal and toxic metals, as the compound of lead or bismuth.A kind of indicating equipment that contains calcium sulfide and ceruse is for example disclosed in U.S. Patent number 3523011.Some patents are the sterilization indicating equipments (for example, those are xeothermic for steam, oxirane, plasma, Peracetic acid, formaldehyde and energy-rich radiation) based on change color, use be inorganic and organic compound, comprise various dye pigment.They comprise following United States Patent (USP):

2798885，2826073，3098751，3098751，3098751，3098751，

3360337，3360338，3360339，3386807，3471422，3568627，

3852034，3862824，3932134，3981683，4094642，4121714，

4138216，4138216，4138216，4195055，4407960，4410493，

4436819，4436819，4436819，4486387，4514361，4514361，

4576795，4579715，4596696，4692307，4678640，5064576，

5087659，5087659，5158363，5200147，5223401，5252484，

5258065，5451372，5451372，5788925，5801010，5866356，

5916816，5990199，6063631，6485978，6589479，6659036，

6800124,6884394,6884394,7141214 and 7189355.

All these patents are included the range of application of this patented claim in.

Prior art discloses the use of metal multivalent compounds but neither one discloses the use of zero-valent metal or alloy (being metal instruction).

The indicating equipment of even now is widely used and low cost, and they all have some shortcomings.The first, ink has a kind of forwarding to and the trend of the tinted article being in contact with it in autoclave.The second, the susceptibility of ink successively decreases in time, especially exists under moist condition, so that initial and last may being affected.Here much other,, for examining and determine the color change systems of moise-heat sterilization, comprise metallic salt, organic acid, oxygenant or other compounds in addition.In them, still have many poisonous, limited change color and/or expensive.Do not have the sterilization indicating equipment of these shortcomings to need.

Pa Teer ink molecules is disclosed in PCT application number #WO 01/10471A1 and with oxirane for monitoring the equipment of sterilization.This equipment is by (a) polymeric binder, (b) reacting ethylene oxide salt, and as sodium thiocyanate and teabrom, and (c) pH sensitive dye, as bromthymol blue and bromcresol purple, mixed coating processes.In the time contacting with oxirane, this equipment at least through change color because material as alkaline in NaOH.But these equipment and molecule are changes colours.

Pa Teer discloses molecule and the equipment of monitoring sterilization with plasma in PCT application #WO 00/61200.This equipment is at least by (a) polymeric binder, (b) plasma activation agent and (c) plasma indicator mixed coating process.When by plasma treatment, particularly when hydrogen peroxide, this equipment is at least through a change color.For example, the phenol red in bonding agent and the coating of teabrom, as be exposed to hydrogen peroxide and due to coloring agent halogenation produce plasma time, polyacrylate through by Huang to blue change color.But these equipment and molecule are changes colours.

Microencapsulation is one fine particle or drop tegillum or coating is surrounded to the process that forms Caplet.The microcapsules here comprise a lot of other similar systems, and as micella, emulsification, disperses lipid and similar phase-separation system.The material of microcapsules inside is called as core, interior phase, or filling material, and outer wall is called as shell sometimes, coating, or film.Between most of microcapsules, there is the diametral distance of little micron and little millimeter.Microencapsulation process is well-known and in U.S. Patent number 2730456,2800457,2986477,3516941,4001140,4081376,4089802,4100103,4105823,4197346,4428982,4444699,4547429, disclosed in 4552811,4622267,6084010 and 6592990.

In thermal response print system, as direct thermal printing, alkaline colour former, acid developer and emulsion are included on a substrate, and when being heated to proper temperature, above-mentioned material melts or softens to react, thereby produces colour-coded.These solid materials are except pigment coating, and bonding agent and adjuvant are included into coating outward.This coating is applicable to surface or other back-up system of paper, as uses the application system of dissimilar coating and dry frosting.Produce image by adopting heat fused and three chromogen material to interact in coating surface processing.

For the material of hot stamping brush and technique at U.S. Patent number: 3539375,3674535,3746675,4151748,4181771,4246318; In 4370370,4388362,4424245,4444819,4470057,4507669,4551738,4682194,4722921,4742043,4783439 and 4942150, disclose.

The development of thermal printer head (independent addressing resistance linear array), has caused the broad development of various thermo-responsive media.In well-known " direct heat " imaging process, the colourless coating on a piece of paper can be become to coloured image with hot, in direct thermal imaging system, carry out colorific variation with several different chemical reactions.Compound in some utilizations is unsettled and in the time of heating, resolves into obvious color.This change color may relate to monomolecular chemical reaction.Heat-sensitive paper also contains thermal response dyestuff, as the azo for developer or recessive dyestuff.Recessive dyestuff is colourless or light alkaline matter, becomes coloured in the time being oxidized with acidic materials (developer).This dyestuff and developer at ambient temperature under the working temperature of Stability Analysis of Structures and the molten thermal printer head at thermal imaging apparatus the material of hot stamping brush and technique at U.S. Patent number: 488705,3539375,3745009,3832212,4243052,4380629,4401717,4415633,4602263,4720449; In 5350870 and 4636819, disclose.

Waveguide is the structure of a guide wave, as optical fiber be that light wave is passed through to dielectric medium.There is in the literature the report of some monitoring equipments based on light wave guiding.It is reported, can change the propagation characteristic of optical waveguide by there is certain chemical reaction on the overlayer on optical fiber.Metallized optical fibre also has report.But, not in the report of the monitoring equipment based on etching metal optical fiber.

The demand of electronics industry is to improve the serviceability of product, as the cost of lower terminal block.Printed board circuit may reside on the Bohemian glass fiber enhanced plastic plate or soft thin slice with the metal level that is used for forming conducting channel connection.At one deck of circuit board, on two layers or multilayer, include interconnective circuit.Can adopt multiple two-plies are bonded together and form a sandwich construction, maybe can be by adding insulation course and circuit manufacture to there is the circuit board of three layers or multilayer in two-ply.

Eas system (EAS) is a kind of committing theft or the technical method of taking away without authorization books in library of retail shop that prevent.Special label is fixed on commodity and books.By salesman to these article proper taking out of or check later these labels are just deleted or were lost efficacy.In the exit in shop, in the time that detection system detects that label is effective, its can sound alarm or other mode is reminded staff.Radio frequency eas tag is exactly a LC oscillatory circuit from 1.75 megahertzes to 9.5 megahertz resonance peaks anywhere in fact.Lc circuit is by multiple resonant circuit or humorous frequency circuit and be made up of an inductor and a capacitor.When linking together, electric current can alternately change in the circuit resonant frequencies between them.Carrying out detuned circuit by destruction partition capacitance device lost efficacy label.Exceed in the high-intensity magnetic field of capacitor breakdown voltage artificial destruction label by label being placed on to the voltage that can produce resonance frequency.

Permanent anti-theft tag is to be coupled on a microwave and an Electrostatic Antenna by a nonlinear element (diode).In exit, an antenna transmission low frequency (approximately 100 kilo hertzs), another sends microwave field.This label is as a signal combination mixer from two field transmittings.This modulation signal trigger alarm.This label is permanent but a little expensive.They are for clothes brand shop mostly.

Now generally adopt the substitute of metallized polymeric films as chrome-faced parts, especially automobile industry.Under normal circumstances, this metallized polymeric films is included in and in two polymeric layers, inserts a metal level.

Typical metallized polymeric films is to be had as NaOH salt or as the metal level of salpeter solution acidic materials and manufactured by etching.Having multiple steps is processes a little dangerous and that pollute.Therefore it is necessary, manufacturing metallic composite by minimum danger and straightforward procedure.

Thin metal foil (between 10-1000 micron) is widely used in various application.Thin metal foil for or on a lot of the said equipments as substrate.In the time that metal forming is used for substrate, it is very thick, generally exceedes the thickness of 10 microns.Etching, includes optionally etching liquid etchant used and is well-known and be widely used and in industry, produce a lot of products.Etching is normally by being immersed in metal part in etchant, as acidity or saline solution.Etching and the dissolving of definition here, comprises as corrosion, gets rusty, and is oxidized and/or is converted into other metal, semimetal, the reaction of the compounds such as semiconductor and alloy.

Metallo-plastic and plastic sheeting are widely used in equally and comprise in molecule and surperficial extensive application because they have electric conductivity and reflective surface.Metallo-plastic film is used as substrate equally in a lot of equipment described here.The metal of fine particle (as, nanosized or larger), as aluminium and bronze (copper, tin, aluminium, the alloy of zinc) are widely used for manufacturing silver, gold and other colored inks and dyestuff (comprising electrically conductive ink, paint and bonding agent).But, not as for monitoring time, Time-temperature, sterilization, humidity, the microwave duration and degree of heating, melt and as plate-making, EAS, electronic equipment, print electronic devices, prints electrode and monitoring equipment based on come the layer very thin to metal or the miscellaneous equipment such as the etched imaging of the super particle of metal with etchant/activator is reported.

The multiple indicating equipment based on metallic compound have a lot of reports but not as described herein for the very thin layer of metal or the report of the indicating equipment of the super particle of metal.Equally, metal plastic film is suggested (as U.S. Patent number: 7430982) as substrate instead of the indicator of indicator.

The etching of metal, as with bronsted lowry acids and bases bronsted lowry, is well-known.Be suggested (as United States Patent (USP) #7361286) for monitoring the indicator that etching finishes.But, there is no the report for the indicating equipment based on metal etch.

Fine metal powder is as aluminium, copper, and zinc, water, acid, the dissolving/destruction/reaction of oxygenant and alkaline metal and alloy thereof is well-known.Recommend to contact to produce with water with its alloying substance with aluminium fine powder hydrogen fuel.Metal etch including aluminium as everyone knows/be dissolved in industry and extensively implement.But not for fine metal powder or as the time, Time-temperature is with sterilization indicating equipment with if the substrates coatings of RFID and eas system (EAS) equipment is as the report of indicating equipment.

Many fine metal powders, such as, it is inflammable that aluminium is considered to.These powder can form explosive mixture with air, especially under wet condition.Dry powder is stable.It is reported, a large amount of aluminium powders or dust contact generation heat that can be spontaneous with water.

In humid air, the aluminium powder of meticulous separation can burn and form inflammable hydrogen.Alumina particles size reduction will increase dangerous.A large amount of moist dust can be spontaneous intensification and form inflammable hydrogen.Aluminium powder is for paint, pigment, and protective coating, printing-ink, rocket fuel, explosive, abrasive material, pottery, inorganic and organic chemical industry and aluminium are as the production of catalyzer.

But, for the combustible metal of superthin layer (as 100 dusts), as aluminium, zinc and their alloy be not as the report of humidity or moise-heat sterilization indicating equipment.

There is no based on ultra-thin/little in the literature opaque and painting layered paper or the etching of marker of label or the report of the indicating equipment of destruction.Need one to be damaged completely and from then on can not revise, the indicating equipment under renovation or recycling in indicator layer.Equally also need an indicating equipment for the seal form of perishable farm products marketing packing box.Some above-mentioned equipment, as need to be to the protection of ultraviolet/sunshine based on diacetylene polymkeric substance (the Temptime company by Mo Lisi Plain, New Jersey sells).Equally also need the indicating equipment of an environment high stability, they can not provide false signal for this reason.In existing technology, these two kinds do not use the indicating equipment of infiltration/barrier layer seldom to have report in induction period.Even use pervious course, its induction period is short and inviolent.Therefore, need to develop one and there is long and violent induction period as the better indicating equipment of " go-do not go " type equipment.Need equally how desired and require performance as the decision-making indicating equipment of anti-amendment, anti-amendment, shows various expiring/completed color, and reading information also forms the image of simple and readability automatically.Here described " expired " or " completing " is instruction, color, and message and picture, layer and/or indicating equipment identical and that occur with them or instruction are expired or completed the process being associated.

In most of the cases, consumer wonders whether product is good, bad, and acceptable is unacceptable, effectively, invalid etc.Some people do not know or can not understand completely good and bad.For consumer's acceptance level, can accept or not accept exactly, seldom there is between.They like self-reading indicating equipment instead of the change color equipment for annotating.Consumer generally wonders whether food is good or bad, fresh or stale, available or unavailable etc.Doctor, pharmacists and hospital generally wonder that medicine is potent or is not potent, effective or invalid, available and unavailable etc. and medical supplies are sterilization or not sterilization.Security personnel generally wonders that visitor/employee is effective or invalid, should allow or should not allow.Therefore, this just needs indicating equipment that a kind of going/the do not go oneself of type reads instead of the reference chart of the elusive color type that gradually changes.

As metal species material be metal, metalloid or there is the metal of the indicator that can be used as one or more system equipments of the present invention of one or more metallic character.Such material and performance comprise below one or more: it can come etching or destruction with activator, also can water, oxygen, acid, alkali and salt are (if flat in said material face, from top to low side, if micro-material, from the outside to the inside/center) react with the activator reacting, through a complicated reaction, it consumes with activator the bundle that finishes, it does not permeate/can not be penetrated into all chemical substances, it does not have (or yet not needing) bonding agent or is coated in without bonding agent on substrate, it is that oneself is bonding, it can contact substrate and not need with bonding agent, its obvious non-conducting, it can be reflective, it is opaque but reflective, it is conduction or semiconductor, it has very high optical density and Thickness Ratio (if optical density when-100 dust thickness is 1), can change its opacity by dissolving, if process is from substantially opaque to completely transparent or semitransparent/transparent variation when thickness is less than 1000 dust, the unexpected optical density that also has below in reaction changes, its atom is bonding by metal attractive force, when forming natural oxide layer or one-tenth oxide layer capable of being combined and/or having opacity to change, there is an induction period.Here term " metallization " refers to and has metallic coating with substrate.Term " metal ", " metalloid ", " metal " and there is metallic character and refer to the instruction material of the indicating equipment that can exchange use.

Term " metal " also comprises that many semimetals and some semiconductive materials, these materials are that oneself is bonding, opaque, carries out various reaction with activator.

Two performances (indicator of the present invention) that metal indicator system is wished are most, with activator or the catalyzer of the equipment based on visual variation, opaque and non-diffusion/various reaction occurs.Metal, semimetal and usually some semiconductors have this two performances.

Indicating equipment of the present invention, as time (TI), Time-temperature (TTI), thaw, freezing, humidity, ionising radiation, temperature, microwave, sterilization (SI) (comprises with steam oxirane, plasma, formaldehyde, xeothermic, hydrogen peroxide and Peracetic acid), chemicals, biological and chemical agent, microwave and every other equipment (as printed circuit board (PCB), RFID and EAS), comprise above-mentioned and defined here, usually indicating equipment or simple equipment or the system of imputed independent or combination here.Indicating equipment or indication mechanism comprise other performance disclosed herein, equipment and process equally.The set that we commonly use in indicating equipment or indication mechanism, unit equipment, sensor, detector, the vocabulary such as monitoring and watch-dog can exchange.

Term indicator comprises dyestuff for any mark too, pigment, bar code, image, information and similar.

The term " variable color " here comprises the variation of optical density (OD), comprises fluorescence, translucence, the variation of the electric conductivity under opacity and transparency and specific environment.

The term " chemicals " here, " chemical agent ", " biological agent ", " chemistry and biological agent ", and simple " molecule agent " is interchangeable, raw material is as water/steam, acid, alkali, with the direct reaction (being activator) of metal indicator or class similar biochemical or chemicals, as oxirane and hydrogen peroxide, react when a kind of proactivator produces another kind of activator, then react with metal indicator.Metal indicator is equally for monitoring these molecule agent and/or technique, as sterilization.Molecule agent is as water/steam, and acid or alkali can be that also vice versa for activator equally.

These information that provide in these chapters and sections of background of invention are all included the scope of the invention in.

Every patent that here above institute describes and quotes involved extendible each instruct molecule, material, technique and disclosed here can be for the manufacture of molecule, material, the equipment of technology and equipment is all included into range of application of the present invention.

[summary of the invention]

summary of the invention and object

Fundamental purpose of the present invention is to provide a kind of to metal material, as metal, semimetal, the thin layer of semiconductor or alloy etc. and/or ultrafine particle carry out in important etched process, monitoring material and process, as the time, temperature, Time-temperature, thaw, freeze, humidity, ionising radiation, microwave, sterilization (comprises steam, oxirane, plasma, formaldehyde, xeothermic, hydrogen peroxide and Peracetic acid), chemistry, biological and chemical agent, electronic equipment, as RFID, EAS, printed electronic, the indicating equipment system and the non-indicating equipment system that print electrode etc.

Another fundamental purpose of the present invention is to provide remarkable change opaque layer or destroys the equipment of impervious formation.

Another fundamental purpose of the present invention is to provide electronic equipment or for support electronic equipment, as printed circuit board (PCB), and antenna, RFID, printed electronic, prints electrode and EAS, utilizes metal micro particles thin layer of etching and a patterned layer.

Another fundamental purpose of the present invention is to provide described equipment is used in etching metal or metal optical waveguide process, measures quantitatively material, comprises chemistry, chemistry or biological reagent.

Another fundamental purpose of the present invention is to provide a kind of indication molecule, and as ink and paint etc. contain metallic material particles, these particles can be used as a kind of indicator and activator after reacting with metal material.

Another fundamental purpose of the present invention is to provide the described indicating equipment being made up of a kind of activator band and indicator strip.

Another fundamental purpose of the present invention is to provide the indicating equipment as indicator by a kind of metal material layer.

Another fundamental purpose of the present invention is to provide the described indicating equipment as indicator by a kind of aluminium, copper, zinc, tin or their alloy.

Another fundamental purpose of the present invention is to provide banded described indicating equipment.

Another fundamental purpose of the present invention is to provide described banded indicating equipment, its sealed box, thus indicate wherein situation and the quality of interiors of products.

Another fundamental purpose of the present invention is to provide described band, and seals a box, contains article processed or monitoring in box.

Another fundamental purpose of the present invention is to provide a kind of described indicating sealing or method of strap or label of monitoring.

Another fundamental purpose of the present invention is to provide a kind of equipment, and it has a substrate, and a thinner metal level, as metal, has an active agent layer on described metal level, and it can obviously change the performance of metal level.

Another fundamental purpose of the present invention is to provide a kind of equipment with substrate, has metal ultrafine particle and change the layer that material formed of metallic particles performance as the meeting such as activator on described substrate.

Another fundamental purpose of the present invention is to provide self termination indicating equipment, and it has a kind of metal and be used as the indicator of intelligent packaging and supply chain management.

The present invention/system also has a fundamental purpose to be to provide a kind of equipment, wherein has an indicating equipment:

There is a long and more violent induction period.

There is a thin and very transparent indicator layer.

There is a reflective indicator layer.

There is a destructible indicator layer.

There is the indicator layer that an electricity is led.

There is an indicator layer without matrix.

There is one without matrix, and thin and very transparent indicator layer.

There is a metal indicator layer.

There is the indicator layer that a metal or metal alloy is made.

There is the indicator layer that a semimetal or semiconductor are made.

There is an aluminium, copper, the indicator layer that zinc or its alloy are made.

Have an opaque indicator layer, it can become transparent after contacting with a kind of activator.

Have an opaque indicator layer, it can become transparent after contacting with activators such as a kind of acid, alkali or salt.

There is an activator or activator precursor layer.

There is a transparent activator or activator precursor layer.

Have a transparent active agent layer, it can induce one significantly to change in indicator layer.

The activator that contains a kind of food or food additive.

Contain a kind of activator, it can make indicator non-conductive, not reflective, transparent or vice versa.

Have an indicator layer, it has the surface of an injustice or embossment.

Have an opaque indicator layer, it can become transparent after contacting with the activator that has food additive.

There is a thin indicator layer made of aluminum, it and a kind of activator or activator precursor are as transparent in become after the contacts such as phosphoric acid, phosphoric acid, phosphorus pentoxide, sodium acetate, sodium thiocyanate, tetraethylammonium bromide, sodium bromide, sodium carbonate, sodium nitrate, ammonium or sodium bicarbonate.

There is the indicator strip of a belt substrate, on a surface of substrate, there is a thin and opaque indicator layer, on another surface of substrate, there is an information or information provides layer.

There is the indicator strip of a belt substrate, on a surface of substrate, there is a thin and opaque indicator layer, being applied of metal has substrate information or information on surface provide layer, and on another surface of substrate, have an information or information provides layer.

There is the indicator strip of a belt substrate, on two surfaces of substrate, all there is a thin and opaque indicator layer.

Have the indicator strip of a belt substrate, have a thin and opaque indicator layer on a surface of substrate, have an information marker on another surface of substrate, wherein said information marker can have different colours, information and/or image.

There is the indicator strip of a belt substrate, on a surface of substrate, there is an active agent layer, on another surface of substrate, there is an information marker.

Have the indicator strip of a belt substrate, on a surface of substrate, have an active agent layer, have an information marker on another surface of substrate, wherein said information marker can have different colours, information and/or image.

There is a permeable or isolation active agent layer.

In indicator layer, there is a permeable or separation layer.

Between active agent layer and separation layer, there is a permeable or isolation active agent layer.

There is permeable or separation layer and an information marker.

Have permeable or separation layer and an information marker, wherein information marker can have different colours, information and/or image.

There is the permeable or separation layer that can protect indicator.

There is the permeable or separation layer of a self-assembling formation.

There is the permeable or separation layer that an oxide or oxyhydroxide form.

Have a permeable or separation layer, it forms after by reactant process metal surfaces.

There is a continuous or discrete permeable or separation layer.

Have a permeable or separation layer, it is self-assembling formation, and be by after reactant process metal surfaces, form or apply form.

There is the separation layer of a rapid wear.

Have a separation layer, it is easily destroyed by a kind of activator or a kind of reagent.

Have an indicator strip equipment, have a substrate in one surface, have a thin and very opaque indicator layer on substrate, this layer additionally also has a permeable or separation layer; On its another surface, there is an information marker.

Have one with separation layer or the permeable layer of active agent response.

There is one and can be activated separation layer or the permeable layer that agent destroys or dissolves.

There is a very transparent separation layer or permeable layer.

There is separation layer or permeable layer that a polymkeric substance forms.

Be made up of multiple activators and indicator strip, by one, permeable layer between thin and opaque indicator layer and band or separation layer form wherein said each indicator strip.

At least there is an artificial indicator and/or artificial indicator layer.

There is an indicator and artificial indicator layer.

Be made up of multiple activators and indicator strip, by one, thin and opaque indicator layer forms wherein said each indicator strip, and wherein activator band is made up of a kind of activator, and also has an artificial indicator layer.

Be made up of multiple activators and indicator strip, by one, thin and opaque indicator layer and a permeable or restraining barrier form wherein said each indicator strip, and it also has an artificial indicator layer.

At least there is one by the bonding coat that in described equipment, each layer is bonded together.

Wherein said bonding coat is pressure-sensitive adhesive.

Wherein said bonding coat is non-pressure-sensitive adhesive.

At least there is the binding of a kind of indicator or activator.

At least having one can releasing layer.

There is a kind of activated indicators.

There is a kind of activated indicators layer.

Be made up of activator and indicator strip, by one, thin and opaque indicator layer and a permeable layer form wherein said indicator strip, and also have an active layer that is used to indicate equipment activity.

There is the permeable layer of a wedge shape.

There is the indicator layer of a wedge shape.

There is the active agent layer of a wedge shape.

There is the preformed layer of a wedge shape.

In indicator layer, there is the permeable layer of a wedge shape.

In active agent layer, there is the permeable layer of a wedge shape.

Between indicator layer and active agent layer, there is the permeable layer of a wedge shape.

There are multiple wedge shaped layer.

Be made up of activator and indicator strip, wherein said indicator strip is made up of the permeable layer of a wedge shape between a thin and opaque indicator layer and band.

Formed by multiple activators and indicator strip, wherein said indicator strip is by a thin and opaque indicator layer, the permeable layer of a wedge shape between band and an information marker composition, information marker can have different colours, information and/or image.

There is an Information Level.

There is a upper Information Level.

There is a lower Information Level.

Between any two-layer in described equipment, there is an Information Level.

There is a upper information marker and a lower information marker.

Have a upper information marker and a lower information marker, they can provide different information.

Have a upper information marker and a lower information marker, they can provide a kind of fresh information.

Having one hides or separation layer.

Having an information hides or separation layer.

On indicator layer, having one hides or separation layer.

With shape.

The band shape of being made up of composition, multilayer and multiple band, have feature as herein described.

Having one deck is image, pattern, bar code or information.

Comprise: one for identifying the barcode label of object or container; One for identify a kind of situation, quality and the Article 2 code labeling of tolerant situation quality; Any one in these two marks is printed on to indicator, and activator, on the arbitrary surfaces of permeable or separation layer or substrate, and changes the method for mark profile.

The present invention also has another object to be to provide a kind of activator composition, and it is made up of a kind of binding and a kind of activator for described metal indicator.

The present invention also has another object to be to provide a kind of activator composition, and it is by a kind of binding, a kind of activator for described metal indicator or precursor, a kind of solvent composition.

The present invention also has another object to be to provide a kind of method of applying contained activator composition in described metal level.

The present invention also has another object to be to provide described equipment, and it has one or more above-mentioned features.

The present invention also has another object to be to provide a kind of indicating equipment, and it can indicate, available, processing, expired, do not use, untreated etc.

Other fundamental purpose of the present invention is activation or assembles above-mentioned indicating equipment.

By changing the scattering of a kind of indicator or marker, opacity and/or reflectivity provide indicating equipment/system and method.

In provided indicating equipment/system and method, using antiseptic material as indicator or activator.

In provided indicating equipment/system and method, can show more than one information.

Provided a kind of wearing and tearing, wear, grind away, wipe broken or damage indicating equipment in, described wearing layer is an opaque layer.

Provided a kind of wearing and tearing, wear, grind away, wipe broken or damage indicating equipment in, described wearing layer is an opaque layer, and under it, is printed on an information.

Provided a kind of wearing and tearing, wear, grind away, wipe broken or damage indicating equipment in, described wearing layer is a metal level, is printed on an information under it.

In provided a kind of wear indication apparatus, the removal that can be worn of one of them opaque wedge shaped layer, or under it, be printed on an information, in wear process, can indicate the instruction degree using gradually.

One of confession control in eliminating equipment, have one for including, the thin metal layer of covering or protective substrate, be removed dissolving this layer after described metal.

The invention provides ultra micro metallic particles, if aluminium, copper, zinc, tin and alloy thereof are as a kind of indicator.

The invention provides ultra micro metallic particles, if the ink of aluminium, copper, zinc, tin and alloy thereof, coating composition and dry coating are as a kind of indicator.

Another fundamental purpose of the present invention/indication mechanism is to provide following method:

Prepare composition as herein described, composition, layer, band and equipment.

Between indicator strip, use activator band, their with or withouts layer as herein described and composition.

Equipment as herein described is applied on an object.

Equipment as herein described is applied on a box.

Equipment as herein described is applied on a human or animal body.

Equipment as herein described is applied on an object that needs monitoring time.

Equipment as herein described is applied on an object that needs monitoring time and temperature.

Equipment as herein described is applied to a human body, in clothes or perishable.

The transparency of the information in equipment described herein or image is changed, and profile or disappearance are monitored.

Read equipment as herein described.

Read equipment as herein described with a machine.

It is that monitoring equipment described herein and they are applied to the term of life in perishable that the present invention also has another fundamental purpose.

The present invention also has another object to be to provide equipment as herein described, and it needn't need liquid.

Another object of the present invention is to provide one equipment cheaply.

Another object of the present invention is to provide the equipment of the automatic reading result of a kind of energy.

Another object of the present invention is to provide the equipment that can cease to be in force automatically.

Other object of the present invention/system is to provide:

A kind of indicating equipment, it can point out step or the process that need to carry out after through a predetermined time.

Warning label on information equipment or mark, or warning label that can dissolve after a schedule time or mark.

A gimmick, it can be replied and within a schedule time, become visible or sightless those inquiries, an information, an image or those problems.

Mark, label or a paster in the past schedule time, can very clearly indicating.

An indicating equipment, the needed times of significant change such as the transparency change that wherein simple and easy or simple member causes can be various.

An indicating equipment, it can be the increase that user clearly indicate the time.

An indicating equipment, it can promptly change color after a specific time interval.

An indicating equipment, it can provide information after one section.

An indicating equipment, it can know and visually indicate shelf-life and surplus in long-time.

Warning label or mark, by there is warning or the passage of the time of warning that disappears in it.

Interchangeable mark, label or a paster, and they need not replace fixed component in the time being replaced.

A shelf-life indicating equipment, when arriving after the specified time interval of shelf life of products, this equipment can change occurs or absent variable color or word.

A persond eixis equipment, it can indicate one long-term period, comprises the moon, or even year.

A time-giver band, it have do not beaten, cut or other process time between everyone, can not change.

A time-giver band, it is suitable for wrist or other joint.

A belt, it can cease to be in force automatically after a time interval.

A product operating period indicating equipment, wherein this equipment is applied on product before Product transport, and this equipment can change in time, indicates the comparative lifetime of product.

The label of a perishable farm products, these perishable farm products comprise that medicine etc. is exceeding the product that can cease to be in force automatically after term of life.

One for client or the boundary belt that ceases to be in force automatically of checking luggage on instrument, and this boundary belt can cease to be in force automatically behind the interval setting, and prevents that it is again printed.

Sensor ceases to be in force automatically.

One cease to be in force automatically stop card, it makes one to stop attendant and can between a very long distance, determine that whether this parking ticket effective.

The transmission ticket ceasing to be in force automatically, transmits and transmission, comprises and manage those when parking, drama and other event tickets that can lose efficacy behind the interval of setting, and comprises day rover, one week ticket, and a monthly ticket and other time interval are prohibited ticket.

A price zone, it can change into the price indicating after a reduction after certain time interval.

One down time indicating equipment, it is disposable, and somewhat expensive.

Automatically a retail label changing, one of them label can be used for buying goods in the point of purchase, and then this label will cease to be in force automatically, thereby can prevent that buyer from reusing this label.

A kind of advertisement or promotion product, after a specific interval time, wherein hiding information can become visible.

A kind of indicating equipment, its can indicate required service after a time interval, can for as more change oil, more oil change, changes water etc.

A kind of indicating equipment, it can indicate product to change after a time interval, as a kind of air strainer, a kind of water filter, battery etc.

An identification marking, it is arranged on and uses district, as a conference centre, in a trade exhibition or in a meeting room.

An identification marking, it can reduce copy, artificial or forge possibility.

An indicating equipment, it is a ticket, after a time interval, can cease to be in force automatically.

An indicating equipment, it is a bar code that meeting ceases to be in force automatically.

A persond eixis equipment, it is not easy to forge.

Warning label or mark, can cease to be in force automatically at information warning described after a specific time interval.

An artificial indicating package band, it indicates a packaging by artificial.

The present invention also has another object to be to provide the indicating equipment that shape is a belt.

Provide a kind of folding indicating equipment.

Provide a kind of method of preparing name label.

Provide indicating equipment, this equipment has a thin metal layer, monitors food boil the metal of degree as a kind of.

Provide the packaging of an Automatic-heating to boil indicating equipment, it is made up of at least one substrate, has at least one metal indicator and at least one activator on this substrate.

Provide the packaging of an Automatic-heating to boil indicating equipment, it is made up of at least one substrate, has the activator that at least one metal indicator and at least one and described metal indicator react on this substrate.

Provide the packaging of an Automatic-heating to boil indicating equipment, it is made up of at least one substrate, on this substrate, have at least one metal level, this metal level is as a kind of metal indicator and a kind of activator that can melt at a certain temperature and react with described metal level.

Provide a kind of microwave energy interactional indicating equipment.

Provide a kind of microwave to boil indicating equipment, it is made up of at least one substrate, has at least one metal indicator and at least one activator on this substrate.

Provide a kind of microwave to boil indicating equipment, it is made up of at least one substrate, has the activator that at least one metal indicator and at least one and described metal indicator react on this substrate.

Provide a kind of microwave to boil indicating equipment, it is made up of at least one substrate, has at least one metal level on this substrate, and this metal level is as a kind of metal indicator and a kind of activator that can melt at a certain temperature and react with described metal level.

Provide a kind of microwave energy interactional indicating equipment, it comprises a microwave energy being supported on the polymeric layer material that influences each other, and one by microwave energy active agent layer and the metal indicator layer that layer supports that influence each other.

Provide a kind of microwave to boil indicating equipment, it is by a polymer fiber layer, and one has thermoplastic polymer's layer of microwave susceptible layer, active agent layer and a metal indicator layer being arranged on microwave energy sensitive layer.

Provide a kind of above-mentioned microwave to boil indicating equipment, it occurs bonding with a complete structure under heat and/or pressure.

Provide a kind of microwave energy interactional indicating equipment, it is by a piece of paper or plank substrate, a polymeric layer, is arranged on a kind of metal on polymeric layer or the interactional sensitive material of other microwave and one in all layers or with the active agent layer of mode diversification in advance.

A kind of microwave susceptible indicating equipment is provided, it comprises that has thermo-plastic polymer material's layer that microwave susceptor material forms, a pattern active agent layer contacting with etching microwave susceptor material and can etching microwave susceptor material, a polymer fiber layer being arranged on above active agent layer, this layer is bonding by heat and pressure and a complete structure.

An interactional indicating equipment of microwave energy is provided, and it is made up of a metal level that is less than 20 dusts.

The food that indicating equipment is boiled for mental package and the microwave of Automatic-heating is provided.

The said equipment and method are provided, and wherein metal level is a kind of metal or alloy.

The said equipment and method are provided, and wherein metal level is aluminium, tin, copper, zinc and alloy thereof.

Provide a kind of microwave energy interactional indicating equipment, its metal or alloy by a kind of low melting point forms.

A kind of temperature indicating equipment is provided, and it is made up of at least one substrate, has at least one metal indicator and at least one activator on this substrate.

A temperature indicating equipment is provided, and it is made up of at least one substrate, has the activator reacting as the metal of indicator with described metal on this substrate.

A temperature indicating equipment is provided, and it is made up of at least one substrate, has a kind of metal as indicator and a kind of activator that can melt in certain predetermined temperature or temperature range and react with described metal on this substrate.

One of object of the present invention is to provide the temperature that a kind of Time-temperature indicating equipment with a metal level produces.

One of the object of the invention is to provide an indicating equipment with metal level, and this equipment can be monitored a predetermined temperature, and can also can monitoring time-temperature in the time reaching described temperature.

One of the object of the invention is to provide lower than environment temperature and Time-temperature indicating equipment, and this equipment has a metal level.

One of the object of the invention is to provide higher than environment temperature and Time-temperature indicating equipment, and this equipment has a metal level.

One of the object of the invention is to provide freezing and Time-temperature indicating equipment, and this equipment has a metal level.

One of the object of the invention is to provide a temperature and time-temperature indicating equipment, wherein uses a kind of metal as a kind of indicator.

One of the object of the invention is to provide a temperature and time-temperature indicating equipment, has wherein used a kind of solid activating agent melting as the metal of indicator with 0 DEG C time.

One of the object of the invention is to provide a kind of indicating equipment using under predetermined temperature, and in the time reaching described temperature, it also can monitoring time-temperature, has used a kind of metal as indicator in equipment.

One of object of the present invention is to provide lower than environment temperature and Time-temperature indicating equipment, has wherein used a kind of metal as indicator.

One of object of the present invention is to provide a kind of freezing and Time-temperature indicating equipment, has wherein used a kind of metal as indicator.

Another object of the present invention is to provide a kind of equipment, and it indicates finally lower than the temperature drift under critical temperature, has wherein used a metallo-plastic film as a kind of indicator.

A temperature indicating equipment is provided, has comprised freezing comprising: (a) metal substrate; (b) active agent layer being arranged on described metal substrate, in the time being cooled to predetermined low temperature, it can discharge a kind of activator.

A kind of method of monitor temperature is provided, has comprised the cooling step in the said equipment.

One of object of the present invention is to provide a temperature and time-temperature indicating equipment, wherein uses a kind of metal as a kind of indicator, and uses one to control release active agent layer.

One of object of the present invention is to provide a temperature and time-temperature indicating equipment, wherein uses a kind of metal as indicator, and controls release active agent layer with a kind of fracture that utilizes microcapsules.

One of object of the present invention is to provide a temperature and time-temperature indicating equipment, wherein uses a kind of metal as indicator, and dissolves or deepen micro-capsule and control release active agent layer with a kind of.

Other fundamental purpose of the present invention is to provide a long indicating equipment with shape.

Other fundamental purpose of the present invention is to provide a long band shape indicating equipment with bonding agent.

Other fundamental purpose of the present invention is to provide an indicator equipment:

Long adhesive tape shape, be applied on perishable box or carton box or be applied to the time and/or responsive to temperature thing on.

As a kind of band.

Band shape, for monitoring the term of life of perishables.

As a kind of band, it has time as herein described, temperature, Time-temperature, thaws, freezing, microwave, humidity, ionising radiation and sterilization and/or other indicating equipment.

A kind of indicating equipment band is provided, and it is made up of an activator band and an indicator strip, forms an indicating equipment band.

An indicator strip equipment is provided, and it is made up of the indicator band applying on activator band.

An indicator strip equipment is provided, and it also has a bonding coat being applied on object.

An indicating equipment is provided, and it is in heating, and pressurization, is activated in radiation and water.

The indicator strip equipment being applied on strap is provided.

The indicator strip equipment being applied under strap is provided.

Provide a kind of indicator strip equipment is applied in to a method on object.

Provide a kind of an indicator strip equipment is applied in to a method on the box that contains perishables.

Provide a kind of indicator strip equipment is applied in to one containing the method on the box of the responsive thing of free, temperature, Time-temperature, humidity and/or steam.

A kind of method that indicator strip equipment is applied to a box of sealing or a packaging is provided.

Provide a kind of by indicator strip equipment be applied to one contain the method on the box processing or monitor.

The above-mentioned indicator strip equipment with a metal level is provided.

A flow process of determining in the different phase of activation indicating equipment is provided.

Provide one or more by a kind of indicating equipment (thering is or do not have a metal level) be applied in one contain in the box of the product element processing or monitor, indicator is accepted significant a variation, after finishing, method obtains the quality of element, determine contact, use, repel or recover, indicator strip is removed or cuts, and product can be accepted or be ostracised.

Instruction distribution system portable and power supply is provided, and it has indicator and activator band, activates them, and the equipment after activation is distributed, and is applied on an object.

A belt divider is provided, the equipment after an activation is distributed, and be applied on an object, comprise the container of perishables or perishables.

A belt divider is provided, the equipment after an activation is distributed, and be applied on a box.

A belt divider is provided, the devices allocation after an activation, in a box of sealing, is contained to more than one perishables element in this box.

A label dispenser is provided, the equipment after an activation is distributed, and be applied on a box.

The present invention also has other fundamental purpose to be to provide:

A sterilization indicating equipment, it is made up of a thin metal layer.

A sterilization indicating equipment, it is made up of a thin metal layer or thin alloy-layer.

A sterilization indicating equipment, it is made up of a thin aluminium, copper, zinc, tin or its alloy-layer.

A sterilization indicating equipment, it is by a 10-10, and the aluminium of 000 dust, copper, zinc, tin or its alloy-layer form.

A sterilization indicating equipment, it is made up of a thin metal layer being arranged on plastic base.

A sterilization indicating equipment, it is by a 10-10 who is arranged on plastic base, and the aluminium of 000 dust, copper, zinc, tin or its alloy-layer form.

A sterilization indicating equipment, it is made up of thin metal layer and extra at least one permeable layer or a separation layer arranging being arranged on plastic base.

A sterilization indicating equipment, it is made up of at least one permeable layer or a separation layer that is arranged on the thin metal or alloy layer on plastic base and be additionally arranged on described metal.

A sterilization indicating equipment, its permeable layer or separation layer by least one wedge shape that is arranged on the thin metal layer on plastic base and additionally arrange forms.

A sterilization indicating equipment, it is made up of at least one permeable layer or a separation layer that is arranged on the thin layer of aluminium, copper, zinc or its alloy on plastic base and be additionally arranged on described metal.

A sterilization indicating equipment, it is by a 10-10 who is arranged on plastic base, and the aluminium of 000 dust, copper, zinc or its alloy-layer and at least one permeable layer or the separation layer that are additionally arranged on described metal form.

A sterilization indicating equipment, it is made up of metal or alloy thin layer and an extra active agent layer that contains arranging being arranged on plastic base.

A sterilization indicating equipment, it is by forming just like active agent layer such as acid, alkali, salt or chelatings metal or alloy thin layer and extra containing of arranging being arranged on plastic base.

A kind of sterilization instruction composition, the activator that it is reacted by a kind of metal or metal alloy particle as indicator and a kind of and described metal or metal alloy.

A kind of sterilization instruction composition, the activator that it is reacted by a kind of aluminium as indicator, copper, tin, zinc or its alloying pellet and a kind of and described metal.

A kind of described sterilization instruction composition that forms a sterilization indicating equipment on substrate that is coated in.

A kind of bag that holds sterilised object that is coated in waits the described sterilization instruction composition on container.

Sterilization indicating equipment described in one, it has characteristic or the feature of TI described herein and TTI.

A kind ofly utilize described sterilization indicating equipment to monitor the method for sterilization.

A method for moise-heat sterilization object, comprises a moise-heat sterilization indication composition with thin metal layer.

A method for moise-heat sterilization object, comprises that has a moise-heat sterilization indication composition that is arranged on the thin metal or alloy layer on substrate.

Monitor a method for moise-heat sterilization object, it comprise one have the thin metal or alloy layer that is arranged on substrate and can with the moise-heat sterilization indication composition of steam reaction.

Monitor a method for moise-heat sterilization object, it comprise one have the thin metal or alloy layer that is arranged on substrate and can with the impaired moise-heat sterilization indication composition of steam reaction.

Monitor a method for moise-heat sterilization object, it comprises that has the thin metal layer that is arranged on substrate can be with steam reaction but moise-heat sterilization indication composition that can dry heat.

A kind of sterilization indicating mixture, it contains a kind of metal indicator and binding, also comprises a kind of binding of polymkeric substance.

A kind of sterilization indicating mixture, it also comprises a kind of surfactant, a kind of defoamer, a kind of filler, a kind of metal indicator, a kind of plastifier, a kind of glidant, a kind of cementing agent, a kind of activator and/or a kind of solvent.

A kind of moise-heat sterilization indicating mixture, it is made up of composition, comprises a kind of metal or alloy, a kind of binding and a kind of activator.

A moise-heat sterilization indicating equipment, comprises a substrate, and it has at least a part mainly on surface, to be coated with described metallic vapour sterilization instruction composition.

A sterilization indicating equipment, it is suitable for being inserted in the disinfection cavity of a forevacuum steam disinfecting apparatus, is used to indicate the existing defective level of the non-solidifying gas that contains metal indicator.

Sterilization indicating equipment, by a kind of metal indicator with as water, water vapour, steam, humidity, moisture, oxirane, hydrogen peroxide, Peracetic acid, formaldehyde, ozone-plasma, ionising radiation and xeothermic composition of reagent in method.

Described sterilization indicating equipment, wherein said activator is prefabricated.

Described sterilization indicating equipment, it has a kind of catalyzer and carrys out catalytic reaction.Described (metal) indicating equipment is applied in to one to be contained on the article or box of having sterilized.

Provide described (metal) indicating equipment is applied on article or container that contain biological waste.

Provide and described (metal) indicating equipment is applied in to one contains by the article or container of steam, xeothermic, oxirane, plasma, Peracetic acid, formaldehyde, ozone and high-energy radiation sterilization.

The present invention also has other fundamental purpose to be to provide:

A kind of ink, pigment, plastisol or paint ingredient, by a kind of microparticle of metal indicator, a kind of medium of a kind of bonding agent and a kind of activator or its precursor composition.

A coating, by a kind of microparticle of metal indicator, a kind of bonding agent and a kind of activator or its precursor composition.

A coating, by a kind of metal, the microparticle composition of a kind of bonding agent and a kind of activator.

A coating, by the microparticle of a kind of aluminium, copper, zinc, tin or its alloy, a kind of bonding agent and a kind of activator composition.

A kind of ink or pigment composition and be arranged on the dry coating on substrate, by the microparticle of aluminium, a kind of binding, a kind of medium and a kind of activator or a kind of precursor, it be can with aluminium, copper, zinc and alloy thereof, acid, alkali or oxygenant that the dry coating on their oxide or substrate reacts.

A kind of with hot water, water vapor, humidity, moisture or high-temperature steam are processed the method for above-mentioned coating.

A kind of with hot water, water vapor, humidity, moisture or high-temperature steam are processed above-mentioned coating, and determine the method that can change the temperature of described coating opacity.

One of object of the present invention be to provide one relatively little, cheap, the described indicating equipment of disposable test bag composition, it can use in forevacuum moise-heat sterilization, exhaust and steam infiltration situation by the routine bag described in simulation Bu Wei-Dick experiment determine whether steam is to work according to suitable standard, thereby to the suitable reaction of surplus air test generation in a forevacuum sterilization.

Another object of the present invention is to provide above-mentioned and relevant object of the present invention, a kind of equipment in vaporium that is suitable for being inserted into of making a profit, and it can indicate the existing defective level of non-solidifying gas.

Metal Packaging indicating equipment is provided; at least one metal indicator that it can be designed activates; as the thin layer of a metal or metal micro particles and at least one activator; wherein have at least a kind of composition to be encapsulated by a separation layer; protection or separation, they just can not react mutually like this.

Metal Packaging equipment is provided, and it at least additionally has a protection, and reaction is permeable, isolation or active layer.

The Metal Packaging equipment of activation is provided, and it can monitoring time, Time-temperature, thaw, freezing, humidity, ionising radiation, temperature, microwave, sterilization (comprising steam, oxirane, plasma, formaldehyde, xeothermic, hydrogen peroxide and Peracetic acid), chemistry, biological and chemical agent and/or electronic equipment, the etched analog of indicator as RFID, EAS, printed electronic and as described in controlling with activator.

Metal Packaging equipment is provided, on two surfaces of its substrate, all there is a thin metal layer and an activator microcapsule layer or prefabricated on metal level.

The activation method of Metal Packaging equipment is provided, and it has destroyed complete described separation layer.

The activation method of Metal Packaging equipment is provided, wherein utilizes pressure, heat, light, laser, moisture, humidity, steam, water and chemicals to activate.

The Metal Packaging equipment using on an object is provided.

The method that provides optical waveguide wave sensor and monitoring chemistry or physical parameter to change, is used the metal optical fiber of a with or without activator or precursor coating to tie up.

Provide optical waveguide wave sensor come monitoring time, temperature, freezing, thaw, Time-temperature, radiation, sterilization, chemistry, reagent, pressure, press etc., they use the metal optical fiber dimension of a with or without activator or precursor coating.

Reagent instruction/monitoring equipment is provided, and its precursor by a kind of metal indicator and a kind of activator forms, for monitoring and the contacting of chemistry or biological reagent.

The described reagent monitoring equipment being used on an object is provided, and it can be monitored and the contacting of a kind of poisonous chemical reagent, and comprises a kind of chemicals as military in activator and never poison etc., as biopreparates such as virus (as anthrax) and bacteriums (as smallpox), as chlorine, chlorine dioxide, ozone, hydrogen peroxide, sulfuretted hydrogen, carbon monoxide, nitrogen dioxide, ammonia, the hazardous chemicals such as hydrazine and humidity/moisture content and oxygen.

Reagent instruction monitoring equipment is provided, and it is made up of a kind of metal indicator of energy monitoring reagent concentration.

A kind of equipment that can prepare printed circuit board (PCB) is provided, and it comprises: one has the substrate of metallic coating, and one is the stopping or separation layer and an active agent layer of printed circuit diagram.

One of object of the present invention is to provide a kind of electronic circuit apparatus, it comprises a substrate with thin metal layer, a prefabricated active agent layer, the metal level of this layer described in can etching, or a figuratum separation layer also can be set between metal level and active agent layer.

One of object of the present invention is to provide the equipment of a multilayer, and it is made up of the multiple selective layers on a substrate, comprises a thin metal layer and activator preformed layer or a figuratum separation layer between metal level and active agent layer.

One of object of the present invention is to provide the equipment of a multilayer, it is made up of the multiple selective layers on a substrate, comprise the activator preformed layer of metal level described in a thin metal layer and an energy etching or a figuratum separation layer between metal level and active agent layer, wherein said activator can thaw and etching after temperature raises.

A kind of equipment of manufacturing printed circuit board (PCB) is provided, has comprised: one has had the substrate of metallic coating, an active agent layer and separation layer and an insulation course that shape is printed circuit diagram.

A kind of method of manufacturing printed circuit board (PCB) is provided, has comprised: prepared a substrate with metallic coating, use an active agent layer that shape is printed circuit diagram.

A kind of method of manufacturing printed circuit board (PCB) is provided, has comprised: prepare a substrate with metallic coating, what to use a shape be printed circuit diagram has stopped or separation layer and an active agent layer.

A kind of method of manufacturing printed circuit board (PCB) is provided, has comprised: prepared a substrate with metallic coating, use active agent layer and an insulation course that a shape is printed circuit diagram.

A kind of EAS equipment is provided, comprises: both sides all have the insulation course of thin metal layer, one is arranged on active agent layer on metal level and one and has the member of circuit diagram.

A kind of EAS equipment is provided, has comprised: both sides have all had the insulation course of thin metal layer, active agent layer and a member that there is circuit diagram and protect apparatus insulated layer being arranged on metal level.

A kind of method that the EAS of preparation equipment is provided, comprising: a metal level is arranged on to each side of insulated substrate, uses band circuit and figuratum separation layer, and use an active agent layer in each side of metal level.

A kind of method that the EAS of preparation equipment is provided, comprising: a metal level is arranged on to each side of insulated substrate, and forms circuit diagram in each side of metal level by an active agent layer.

A kind of method that the EAS of preparation equipment is provided, comprising: a metal level is arranged on to each side of insulated substrate, and uses an active agent layer in each side of metal level, etch metal layers forms circuit diagram.

A kind of method that the EAS of preparation equipment is provided, comprising: at the two-layer formation conducting channel figure of insulation course, and every one deck of insulation course has a metal level, and utilizes a kind of activator to bring etching.

A kind of EAS equipment is provided, and it is made up of the circuit diagram being arranged on insulated substrate, and these circuit diagrams are the electronic article surveillance tag circuit that are used in wireless radio frequency circuit.

The present invention also has other fundamental purpose to be to provide:

An activator band that can react with conductive surface.

Activator band is used in a method on electronic equipment by one.

Activator band is used in the method on conductive path in an electronic equipment by one.

Activator band is used in the method on conductive path in an electronic equipment or layer by one.

One with electronic equipment in conductive path or the activator band that reacts of layer.

An activator band, in the time that it reacts, can destroy or reduce the electric conductivity of conductive path in electronic equipment or layer.

One can react with conductive layer, forms the activator band of wire.

A kind of activator or an activator band, it can make equipment on different paths, lose efficacy or reply from after a conductive path reaction.

Activator band is applied in a method in embedded RFID equipment by one.

Method on an antenna that activator band is used in to conductive path in RFID equipment.

An activator band, it can react with the antenna of RFID equipment or conductive path, reduces or destroy the electric conductivity of path.

An activator band, it can react with the antenna of RFID equipment or conductive path, reduces or destroys electric conductivity, makes equipment not readable.

An activator band can form an antenna in the time that it is used in a metal level from a conductive layer.

One has the RFID equipment of two RFID inlays, and one of them has the activator band that can destroy its conductive path.

Manufacture the method for RFID equipment for one, activator band is used in a conductive surface by it, and this surface has a patterned separation layer.

One is read the method for RFID equipment before and after activating or before and after the deactivation.

One is read the method for RFID equipment after forming antenna.

The RFID equipment after activation is used in a method on object by one.

By RFID equipment as time, temperature, the Time-temperature that comprises monitoring reagent of the present invention, thaw, freezing, microwave, humidity, ionising radiation and sterilization and/or other indicating equipment.

A kind of metallization pattern composition is provided, comprises: one has the polymeric layer of thin metal layer, noncontinuity active agent layer and a protectiveness polymeric layer with pattern formation design.

A kind of metallization pattern composition is provided, comprises: one has the polymeric layer of thin metal layer, a patterned separation layer, an active agent layer and a protectiveness polymeric layer.

A kind of metallization pattern composition is provided; comprise: one has the polymeric layer of thin metal layer; one with pattern and form the noncontinuity active agent layer of design, and composition is adhered to the bonding coat on a substrate and polymeric layer by protectiveness polymeric layer and one.

Described metallization pattern composition is provided, and wherein said layer is all aluminum.

Described metallization pattern composition is provided, and wherein said bonding coat is all by a kind of pressure-sensitive, and heat activated adhesive or radiation-curing binders form.

Another object of the present invention is to provide a kind of toy of being made up of described indicating equipment, novelty, information, Gift Card, greeting card etc.

A further object of the invention is to provide polymer adhesive, emulsion, latex and the solvent that described equipment uses, and described equipment can self-crosslinking or can be crosslinked with adjuvant.

A further object of the invention is to provide emulsion, latex and the bonding agent that described equipment uses, and described equipment is not subject to the impact of humidity sterilization and moise-heat sterilization.

A further object of the invention is to provide the neutral or closely neutral polymer solution of the pH value using as the bonding agent of described equipment.

A further object of the invention is to provide the polyurethane and the carboxylated polypropylene acidulants/polyacrylate that use as the bonding agent of described equipment.

A further object of the invention is to provide at least one indicating dye of described equipment use or the potpourri of pigment.

A further object of the invention is to provide the color indicator of different performance or the potpourri of non-indicative pigment or dyestuff that described equipment uses.

The substrate or the similar layer that provide a kind of the said equipment to use, it is formed by tygon, polypropylene, a kind of ionomer, polyvinyl fluoride, polyvinylidene chloride, acronitrile-butadiene-styrene, polyvinylidene fluoride, TPO, thermoplastic polyurethane, Polyvinylchloride, poly-ethylethylene ester, polyester or polyamide.

The bonding agent or the similar layer that provide a kind of the said equipment to use, its by one pressure-sensitive or heat sensitive adhesive make, described bonding agent comprises acrylate pressure sensitive adhesives, silicone pressure-sensitive adhesive, heat-activatable adhesive, polyester and isocyanate adhesive, neoprene and isocyanate adhesive, polyurethane and isocyanate adhesive, polyurethane and aziridine bonding agent.

The metal or the similar layer that provide a kind of the said equipment to use, comprise zinc, tin, gallium, aluminium, magnesium, cadmium, copper, nickel, cobalt, iron, stainless steel, gold, platinum, chromium, palladium, rhodium and their alloy.

Also provide and in the said equipment, had at least one deck larger than the other parts of equipment.

A kind of equipment and method that reads described indicating equipment is also provided, comprised bar-code reader, spectrophotometer, optical density or the linear charge-coupled device (CCD) that can detect described variation.

The precursor of described activator is also provided.

The activator using in described indicating equipment precursor is also provided.

The precursor using in the products such as acid, alkali, salt is also provided.

The precursor of described activator is also provided, its for time, temperature, Time-temperature, thaw, freezing, humidity, ionising radiation, microwave, sterilization (comprising steam, oxirane, plasma, formaldehyde, xeothermic, hydrogen peroxide and Peracetic acid), chemistry, biological and chemical agent and electronic equipment, as RFID, EAS, printed electronic, print electrode etc.

The method and the member that from precursor, produce activator product are also provided.

One of object of the present invention is to provide a kind of indication mechanism, and it overcomes shortcoming of the prior art more violent induction period relatively by providing in instruction event.

A further object of the invention is to provide the instruction that described system reads instruction event or object simply.

A further object of the invention is to provide a kind of indication mechanism, and it can mark a specific event or one and recur the progress of event.

A further object of the invention is to provide a kind of system, and it can produce an information, warning, detailed introduction, shelf-life.

A further object of the invention is to provide the indication mechanism that a kind of meeting ceases to be in force automatically or stops.

Indication mechanism involved in the present invention can be used in various indicating equipments.

[brief description of the drawings]

Below will be by embodiment, above-mentioned and other object of the present invention is described by reference to the accompanying drawings, feature and advantage.Describe the present invention in detail below in conjunction with accompanying drawing:

Fig. 1 is the cut-open view of the indicating equipment of a kind of (a) of the present invention and existing (b).Fig. 1 (c) is the cut-open view of metal level, wherein in metal level, is provided with the oxide skin(coating) of natural formation.In other figure, do not show ultra-thin oxide skin(coating).

Shown in Fig. 2 is that color is with respect to the variation diagram of time by after the present invention (a) and the activation of existing instruction (b) equipment.

Fig. 3 is bottom in equipment and the structural representation of optical layers.The described oxide skin(coating) that is arranged on the natural formation on metal level is not shown in the diagram.

Fig. 4 is cut-open view (a) and the vertical view (b) that the indicating equipment after a kind of activation is in different phase.In figure, do not show the dissolving of metal oxide layer.

Fig. 5 is cut-open view (a) and the vertical view (b) of a kind of indicating equipment (1) rear (2) before termination, is provided with the termination indicator layer of information in this equipment.

Fig. 6 is cut-open view (a) and the vertical view (b) of a kind of indicating equipment (1) rear (2) before termination, is provided with the termination indicator layer of provided with bar code in this equipment.

Fig. 7 is cut-open view (a) and the vertical view (b) of a kind of indicating equipment in termination front and back (2), is provided with information and another information being printed in termination indicator layer being printed in described active agent layer and forms a new information in this equipment.

Fig. 8 is provided with (b) and is not provided with in a kind of indicating equipment of (a) pervious course the structural representation of some basic selective layers.

Fig. 9 is after described equipment activates, color is the variation diagram with respect to the time with respect to the variation diagram of time or transparency, wherein said equipment is not provided with a pervious course (a), and is provided with more (b) or the pervious course of (c) still less.

Figure 10 is cut-open view (a) and the vertical view (b) that the indicating equipment after a kind of activation is in different phase, is provided with the pervious course of a wedge shape in this equipment, has and be printed on a colored number stopping in indicator layer on pervious course.

Figure 11 is a structural representation that automatically stops the mark (time-giver) of accessor, and it is provided with the nontransparent activator substrate of colour and a permselective layer of a dark X of its upper printing; (a) cut-open view of mark, (b) use in accessor overhead view image and (c) stop after overhead view image.

Figure 12 is the cut-open view that is provided with the indicating equipment of the disconnected property of various differences layer in diverse location and junction, position.

Figure 13 is the cut-open view of two kinds of possible variations of a band shape or collapsible indicating equipment, and wherein the substrate end of equipment is provided with activator and indicator strip.

Figure 14 is the cut-open view of the possible variation of the another kind of a band shape or collapsible indicating equipment, and wherein equipment is provided with a major part of substrate, and this part is hidden by an indicator layer after folding/activation (b) front (a).

Figure 15 is a kind of cut-open view (a) and vertical view (b) of indicating equipment, this equipment is provided with the separation layer (a kind of etching face) of an X-shaped in indicator layer, when after (1) activation, the equipment after (2) stop and after (3) termination has a colored indicator layer that stops.

Figure 16 is the cut-open view of a part in the biobelt dispenser that the belt after activation is cut apart.

Figure 17 has been sealed by a tape dispensers from one, and with the box of indicating equipment after activation, as the structural representation of perishables is housed.

Figure 18 is by the structural representation of a box of indicating equipment (a) sealing after a kind of activation, its on an indicator strip and the termination of indicating equipment (b) be provided with an activator band.

Figure 19 is the cut-open view of an instruction/band of some preferred features of a kind of TTI of having, and this belt is to be arranged on for different objects on a substrate, and the same side of this substrate is provided with active agent layer and conventional psa layer.

Figure 20 is the cut-open view of an instruction/band of some preferred features of a kind of TTI of having, and this belt is to be arranged on for different objects on a traditional band.

Figure 21 is a kind of being arranged on a conventional band, the cut-open view of a band of suitable feature of some with TTI.

Figure 22 is a kind of being arranged on a conventional band, have a pair of feature of TTI a band analyse and observe (a) vertical view and (b) cut-open view.

Figure 23 is a kind of vertical view of method of the RFID of preparation indicating equipment.

Shown in Figure 24 be the RFID that do not establish activator band (a) embed and one be applied in antenna (b) and (c) the activator band at diverse location place.Be provided with the RFID equipment that two RFID embed, one of them is provided with an activator band as shown (d).

Shown in Figure 25 is that RFID in Figure 24 is embedded in the structural representation being activated after agent band etching part antenna.

Figure 26 is (a) a kind of dual damascene RFID indicating equipment, (b) has activator band using and make to embed the cut-open view after not can read during (c) at etching antenna in RFID embeds.

Figure 27 is the ink coating of (a) a kind of metallic particles and a kind of binding, (b) metallic particles and a kind of activator, (c) the activator generation partial reaction on metallic particles and cut-open view that (d) metallic particles is destroyed completely.

Shown in Figure 28 is method and different times (d-f) structural representation of this equipment after activation of preparation (a-c) a kind of thermoplastic activable indicating equipment, and this equipment has a thermoplastic being arranged on metal level and can activate and pack into the active agent layer of micro-capsule.

Figure 29 be the activable indicating equipment of a kind of thermoplastic (a) and after activation (b) and stop time (c-d) structural representation, this equipment one side has a thermoplastic being arranged on metal level and can activate and pack into the active agent layer of micro-capsule, and opposite side is provided with conventional hot stamping layer.

Figure 30 is a kind of preparation by the cut-open view of the method for the folding direct hot stamping indicating equipment obtaining.

Figure 31 is a kind of micro-capsule activator, and a kind of indicator and a kind of adjuvant are applied in a cut-open view in indicator layer by different way.

Figure 32 is vertical view (a) and the cut-open view (b) that RFID embeds, this RFID embed (a1 and b1) be provided with one RFID embed (a2 and b2) and the micro-capsule activator belt of (a3 and b3) when termination.

Shown in Figure 33 be in inductance process and inductance process after can show the example of the TTI equipment of two information.

Shown in Figure 34 is the example that is provided with the mobile isolation indicating equipment of a wedge shape infiltration isolation.

Shown in Figure 35 be when activation (a) and termination time (b), the example of the box being sealed by an indicating sealing band.

Figure 36 is the example of visitor's pass of the different times after activation, and described being marked at is provided with a wedge shape pervious course between indicator and active agent layer.

Example when Figure 37 is the different times of a RFID indicating equipment that is provided with activator band after activation.

Figure 38 is the example for a RFID and an antenna of its similar electronic equipment formation.

Figure 39 is the transparent number percent time history plot of indicating equipment.

Figure 40 is the instance graph of a moise-heat sterilization indicating equipment, and wherein said equipment is to be made up of a kind of aluminium powder and a kind of activator, and described aluminium powder and activator were all processed under different conditions for sterilization.

Figure 41 is the instance graph of the moise-heat sterilization indicating equipment of a mobile isolation, and wherein said equipment is to have sterilized the different time at 120 DEG C.

Figure 42 is the instance graph of a disinfectant with hydrogen peroxide indicating equipment, and wherein said equipment is to be made up of a kind of aluminium powder and a kind of precursor, and described aluminium powder and precursor were all processed under different conditions for sterilization.

Figure 43 is the instance graph of an oxirane disinfection indicating equipment, and wherein said equipment is to be made up of a kind of aluminium powder and a kind of precursor, and described aluminium powder and precursor were all processed under different conditions for sterilization.

Figure 44 is that phosphoric acid makes a kind of aluminium lamination start to become almost transparent, and along with the variation of concentration becomes transparent curve map completely.

[embodiment]

embodiment

The present invention relates to a kind of indication mechanism that can use in various indicating equipments.

Indication mechanism of the present invention is made up of a metal indicator layer and an active agent layer, and wherein said metal level is a kind of metal, metal alloy, semi-metallic or semiconductor material.Described activator is the reagent that a kind of characteristic that can utilize etching or destroy indicator layer or change this layer irreversibly changes this layer,

Indicator layer of the present invention comprises a kind of metal maybe can with electric conductivity, reflectivity, high opacity, automatic bonding and/or barrier properties that had, it can become non-visible, transparent, translucent, non-conductive or contact with described activator after can be destroyed.

The preferred indicator material of the present invention comprises a kind of metal, as alkaline metal, earth alkali metal, transition metal, late transition metal, group of the lanthanides and actinide metals or their alloy, or preferred low melting point metal, copper and alloy.

Preferred metal comprises aluminium, tin, zinc, copper, manganese, magnesium, nickel, cobalt, iron, sodium, potassium, lithium, calcium, gallium, caesium, germanium, indium, silver or their alloy, more preferably aluminium, copper, zinc or tin.

The preferred metal of the present invention and metal alloy comprise that those are to water, acid, alkali, chemistry or biopreparate and salt-sensitive metal and metal alloy.The alloy that also can use various metals to form, as aluminium-magnesium-copper.Can use many books, as " aluminum and its alloy ", Joseph R Davis, J.R. Davis affiliated company, the ASM world, material garden, OH, the aluminium alloy described in 1993 is manufactured indicator.

Industrial various different aluminum copper mixtures, the mass content of aluminium is 5%-11%, remaining is copper or other alloying component, as used in the present invention iron, nickel and silicon.Aluminium and other copper, as copper-zinc also can be used as indicator.

Activator of the present invention comprise all in indicator compound can and indicator reaction, produce the composition of an irreversible change.Activator of the present invention more preferably comprises acid, alkali, salt, chemistry or biological products, complex compound, the composition of the quick corroding metal of the energy such as water and oxygen and its alloy.The present invention has also comprised the precursor of activator, those can with indication mechanism in other composition effect produce the composition of activator of the present invention.

In a preferred embodiment, activator is mineral acid, as phosphoric acid, phosphorous acid, hydrochloric acid, nitric acid, sulfuric acid, sulfonic acid, carboxylic acid, their precursor or their potpourri.

In another preferred embodiment, activator is the kation of a kind of metal hydroxides, metal alkoxide, aryloxy group metal or nitrogen.

In another preferred embodiment, activator is a kind of weak acid strong alkali salt, a kind of strong acid weak base salt, a kind of strong acid and strong base salt or a kind of weak acid and weak base salt.

In another preferred embodiment, activator is monovalence, divalence or trivalent metal or nitrogen, sulphur, phosphorus, the halogenide of halogen, oxide, nitrate, nitrite, phosphate, phosphite, phosphate, silicate, sulfate, hydrosulfate, sulphite, sulfide, disulfide, sulfonate, cyanate, prussiate, thiocyanate, acetylacetonate, carboxylate, percarboxylic acids salt, carbonate or supercarbonate, or their potpourri, for example methyl ammonium bromide, ammonium thiocyanate, lime chloride, cupric chloride, cupric ammine complex, diacetone lithium, lithium chloride, lithium formate, phosphorus, phosphorus pentoxide, potassium acetate, Potassium Benzoate, potassium bromide, potassium chloride, potassium ferrocyanide, the potassium ferricyanide, sylvite, sodium acetate, sodium bicarbonate, sodium bromide, sodium carbonate, Zassol, sodium diethyl two, sodium iodide, sodium metasilicate, sodium nitrate, sodium sulphite, sodium tetrafluoroborate, sodium tetraborate, sodium thiocyanate, sodium thiosulfate, tetraethylammonium bromide, zinc chloride or their potpourri.

Preferred activator comprises a kind of chelate or complex of metal cation, as a kind of filtering metal kation, and the complex of amine and cupric chloride, or the complex of amine and nickel chloride, or the complex of ammonia and cupric chloride, or the complex of ammonia and nickel chloride.

A preferred embodiment of the present invention relates to a kind of indication mechanism, comprising: a) a kind of metal indicator layer; With b) a kind of contact with indicator layer or approaching activator precursor.In the equipment that this embodiment comprises, described activator is oxygen, the water of ambient humidity or vapor form, gas-phase reagents or microwave, wherein said activator or its precursor utilize a band or other application directly and metal level reacts, and do not need directly to contact with metal level.Preferred, a thin metal layer, as a metallo-plastic film, can be for monitoring as the chemicals such as water and toxic chemical, wherein said water and toxic chemical are as the metal interaction on activator and plastic sheeting.In this indication mechanism example of the present invention, activator is a kind of active agent layer that there is no binding.In indication mechanism claimed in claim 1, described activator or precursor layer are before it contacts with a kind of monitoring reagent or enter before a monitoring process, can not react with indicator.

In a preferred embodiment, described reagent is moisture, steam, oxirane, formaldehyde, ozone, Peracetic acid, hydrogen peroxide, chemical agent or biopreparate.Another embodiment of the present invention relates to a kind of indication mechanism, comprising: a) a kind of metal indicator layer; And b) a kind of activator or activator precursor being arranged on described metal indicator layer.The present embodiment comprises a kind of equipment, wherein on metal level, is provided with a dry coating for sterilizing, and this dry coating is can not react with indicator before contacting with a kind of reagent, and described reagent can be steam, oxirane, hydrogen peroxide etc.Described indicator layer can be arranged on as on the substrates such as plastic sheeting.

At another embodiment, described indicator layer is arranged on a substrate, and wherein said substrate is a plastic sheeting, and this substrate has the continuous metal layer that a thickness is less than 10,000 dusts.Described indicator layer normally thickness is less than continuous metal layer or the stratum granulosum that thickness is less than 10 microns of 1,000 dust.

Another preferred embodiment of the present invention relates to a kind of indication mechanism, comprising: an a) metal indicator layer; And b) a kind of activator maybe can produce the precursor of activator; C) a kind of binding of activator; And d) a kind of binding that active agent layer and indicator layer are glued together.In this embodiment, indicator layer is to be attached on a substrate, and this substrate is a plastic sheeting with contact adhesive.

Another preferred embodiment of the present invention relates to a kind of indication mechanism, comprising: an a) metal indicator band; B) an activator band; Wherein said indicator strip comprises a substrate, and this substrate at least adheres to mutually with a metal level; Described activator band comprises that a kind of activator maybe can produce the precursor of activator, and this activator or its precursor are dissolved or be dispersed at least one hypothallus.

The present invention also has an embodiment to relate to a kind of indication mechanism, comprise: the composition of an indicator strip and an activator band, they are at least bonded together with a kind of bonding coat, and wherein said indicator strip comprises a substrate, and this substrate at least adheres to mutually with a metal level; Described activator band or the precursor band that contains a kind of meeting generation activator are made up of a substrate that contains a kind of activator, and wherein this substrate at least adheres to mutually with a metal level.

Another preferred embodiment of the present invention relates to a kind of for monitoring the indication mechanism of a kind of material or a process.More preferably, the material in described indication mechanism is a kind of chemicals, a kind of chemical reagent or a kind of biopreparate or its potpourri; Described process is the time, temperature, and Time-temperature, freezing, thaw, cooling, humidity, boils food, microwave, pressure, radiation, comprises steam, oxirane, hydrogen peroxide, hydrogen peroxide plasma, the sterilization that xeothermic or ionising radiation is carried out.

In another preferred embodiment of the present invention, described indication mechanism is the situation that is used to indicate perishables, wherein said perishables are a kind of food, as fresh, refrigeration or freezing vegetables, fruit, meat, fish, poultry, dairy produce, cure product, fruit juice, the food that boils in advance, soft drink, alcoholic beverage or as non-food stuffs such as medicine, vaccine, biological sample, cosmetics, reactive compound, biogenetic products, battery, X-ray film or sensitive films, wherein biological sample can be serum, blood or blood plasma.

In another preferred embodiment of the present invention, described indication mechanism be for, a for example safety label, the retail label of self-timing, biological industry process monitor, prevent reusable automatic termination label, safe ID label, visitor's card, the automatic end mark of stopping, packaging and shipping label, wrist strap, train, motorbus, site activity, the time explanation ticket of theater, go sightseeing, emergency ward, hospital, museum and other places, the automatic termination card of runway passway, the luggage checking by specific project on airport, wallet, the safety label that chest screens by inspection, with at unattended but by visitor's entrance of video management automatically send stop visit electronic tag.In addition, described indication mechanism can be used for monitoring client the time limit of article, comprises without limitation beverage, food, health products, personal or household products.What also comprise is the application of " novelty " type, as toy, novelty, information, pattern, pattern, Gift Card or greeting card.

In another preferred embodiment of the present invention, described indication mechanism is for pharmaceutical preparation, food or biological waste, or for monitoring the sterilization of these products.

In another preferred embodiment of the present invention, described band is also provided with an adhesive phase, and it is attached on a monitored object described indicator layer.

In another preferred embodiment of the present invention, indication mechanism of the present invention can be used as a kind of RFID or printed circuit board (PCB).The present invention more preferably relates to a kind of equipment, and it comprises a substrate with a thin metal layer, and what isolated material was made has patterned layer and an active agent layer.After described system is activated, isolated material can be protected figuratum region in indicator layer, and making patternless region in metal level is that an electronic equipment or a metal pattern at least form a conductive path.In this external preferred embodiment, an electronic equipment comprises that a RFID who is connected with electronic chip embeds or conductive path, and the active agent layer in this electronic equipment can be destroyed a conductive path of indicator, thereby destroys this electronic equipment.Relate in addition a kind of EAS equipment, its active agent layer that insulation course with thin metal layer and both sides are equipped with by one forms.

Indication mechanism of the present invention has a kind of information at least, and this information is color, word or the mark that is displayed at least described marker one side.Described information can be colored.The both sides of indicator layer can be provided with an information.In some implementations, described system has at least two kinds of information, and these two kinds of information can not start to show simultaneously.In one embodiment, when described indication mechanism processing in a things or before, the first demonstration information can be indicated situation or the quality of this things, and the second demonstration information can show individually information or show in combination information with the first instruction situation or the quality of this things after processing this things, as the degree of not boiling of a things of first information instruction, freshness, usability, acceptability; And the second demonstration information the processed rear independent instruction of this things or processed with this after things first instruction degree of boiling, rotten, unavailability, inadmissibility combines, or the first information indicates this things not sterilize, unavailable, do not check and accept, and the second information the processed rear independent instruction of this things or with the degree of boiling of the first instruction, aseptic, availability and acceptability combine.

In another preferred embodiment of the present invention, indicator layer of the present invention is made up of ink, pigment, gel and plastisol etc.Described metal indicator layer is graininess, and has or do not have solvent medium.Preferred, an embodiment contains the compositions such as ink, pigment, gel and plastics, this example comprises: a) b) described activator and c) a kind of binding (dry coating, as solvent-free) being used on substrate of described graininess indicator.Another embodiment comprises an indicating equipment, and it can monitor (1) a kind of material, can be a kind of chemicals, a kind of chemical reagent or a kind of biopreparate or its potpourri; (2) processes, can be the time, temperature, and Time-temperature, freezing, thaw, cooling, humidity, pressure, radiation, comprises steam, oxirane, hydrogen peroxide, hydrogen peroxide plasma, the sterilization that xeothermic or ionising radiation is carried out.

In another embodiment of described indication mechanism, described active agent layer comprises a kind of activator precursor, as a kind of acid, alkali or salt.An embodiment of precursor is phosphorus pentoxide, in the time that it and water etc. react, can produce phosphoric acid.

An alternative embodiment of the invention comprises the precursor that a kind of described precursor uses, and as white or yellow phosphorus, in the time that it and oxygen react, can produce a kind of precursor phosphorus pentoxide, and phosphorus pentoxide react with water can generation activator phosphoric acid again.

Other precursor of activator can be a kind of halogen monomer or a polymkeric substance, halogenide, sulfonium or phosphorus compound.

An alternative embodiment of the invention relates to indication mechanism of the present invention is applied in to a method in target, wherein in this target, contains processed or monitored object.

An alternative embodiment of the invention comprises a kind of system, wherein in this system, one or more extra plays are increased, described extra play can be a known binding layer, a permeable active agent layer, a permeable active agent layer of wedge shape, an isolation active agent layer, a reaction, can destroy or degradable separation layer, one stops marker, an amendment marker, one is activated marker, information or image formation layer, information or separation of images layer, information or image are removed layer, the oxide skin(coating) of a self-assembling formation, a stealthy layer, can active coating, a microcapsule layer or a thermal printing layer etc.

The present invention also has another embodiment to comprise an indicating sealing band, and it is provided with two band dispensers that are used to indicate agent band and activator band, and in the time described band being applied on a container, two described bands are cut apart simultaneously.

Be printed in indication mechanism of the present invention, the mode on a substrate of this system of being especially printed on can be temperature-sensitive print, be more preferably directly thermal printing.

Any layer in described indication mechanism can comprise an information or in any side of every one deck all with an information.

Another embodiment is a kind of indication mechanism, described indicator layer or system activation evergy required time that changes is changed or is adjusted by one or more parameter of lower number: the thickness of active agent layer, the thickness of indicator layer, the thickness of permeable layer, the concentration of activator, the concentration of precursor, a kind of concentration of adjuvant in activator, a kind of concentration of adjuvant in permeable layer, a kind of solvent, the character of surfactant and catalyzer, the character of active agent layer, the character of indicator, the character of permeable layer, the character of additive layer, the character of catalysts and retarding agent.

An alternative embodiment of the invention is a kind of optical waveguide monitor of pinpoint accuracy, an electronic circuit or an EAS.

The invention also discloses a kind of indication mechanism, this system is a safety label, the retail label of self-timing, biological industry process monitor, prevent reusable automatic termination label, safe ID label, visitor's card, the automatic end mark of stopping, packaging and shipping label, wrist strap, train, motorbus, site activity, the time explanation ticket of theater, go sightseeing, emergency ward, hospital, museum and other places, the automatic termination card of runway passway, the luggage checking by specific project on airport, wallet, the safety label that chest screens by inspection, with at unattended but by visitor's entrance of video management automatically send stop visit electronic tag.

In another embodiment, described indication mechanism is toy, novelty, information, pattern, pattern, Gift Card or a greeting card.

In another embodiment, described indication mechanism is a part of RFID, EAS or printed circuit board (PCB).

An alternative embodiment of the invention is a kind of method of monitor drug, food or biological waste situation, and it comprises described indication mechanism is arranged in the external packing of these medicines, food or biological waste.

The present invention also has another embodiment to relate to monitoring whether to contain a kind of toxic chemical, and the method for reagent or water, comprises described indication mechanism is arranged on to monitored area, and from this indication mechanism obtaining information.

Another embodiment is a kind of method of monitoring perishable, and it is that described indication mechanism is arranged on perishable or near it, and described perishable is a kind of food or a kind of non-food.Preferably monitor client and use the method in article time limit by monitoring articles, wherein said article be open or in use or used certain hour, described article are beverages, food, health products, personal or household products.

The present invention also relates to a kind of method of preparing indication mechanism of the present invention.In one embodiment, the present invention presses to an activator band on a metal indicator band, thereby makes indicator strip of the present invention.In another embodiment, an active agent layer is coated on a metal indicator layer, and this metal indicator layer can be provided with, and a pervious course also can be set.In another embodiment, can in described indication mechanism, increase extra play.

The present invention also has an embodiment to relate to for detection of and detects quantitatively or monitoring chemistry, biochemistry or biological reagent, and this system is to use in the process of etching metal or Metallic Optical Waveguide.Chemical reagent comprises a kind of fatal reagent, a kind of frothing agent, one affects Blood Preparations, a kind of never poison, a kind of lung reagent, a kind of anergy reagent or a kind of riot control agent are as cyanogen chloride, hydrogen cyanide, ethyl dichloroarsine, methyl dichloroarsine, phenyldichloroarsine, lewisite, 1, the chloro-3-ethyl thioether of 5-bis-, 1, two (the 2-chloroethyl sulfenyl) ethane of 2-, 1, two (the 2-chloroethyl sulfenyl) n-propanes of 3-, 1, two (the 2-chloroethyl sulfenyl) normal butanes of 4-, 1, two (the 2-chloroethyl sulfenyl) n-pentanes of 5-, 2-chloroethyl chloromethyl thioether, two (2-chloroethyl) thioether, two (2-chloroethyl sulfenyl) methane, two (2-chloroethyl sulfidomethyl) ether, two (2-chloroethyl sulfidomethyl) ether, two (2-chloroethyl) ethamine, two (2-chloroethyl) methylamine, three (2-chloroethyl) amine, tabun, sarin, rib is graceful, cyclosarin, GV, VE, VG, VM, VR, VX chlorine, chloropicrin, phosgene, azobenzene, (BZ) 15 doses, 3167 doses of EA, nauseant, capsicum water spray, CS gas, CN gas or CR gas etc.Chemicals comprises acetone cyanohydrin, acryl aldehyde, vinyl cyanide, vinylcarbinol, allylamine, allyl chlorocarbonate, allyl group isosulfocyanate, ammonia, arsenic trichloride, arsine, Boron tribromide, boron chloride, boron trifluoride, bromine, bromine chloride, BPF, bromine trifluoride, carbon disulphide, carbon monoxide, carbonyl fluoride, cos, chlorine, chlorine pentafluoride, chlorine trifluoride, chloroacetaldehyde, chloro-acetone, chloroacetonitrile, chloracetyl chloride, chlorosulfonic acid, crotonaldehyde, cyanogen, 1, 2-dimethylhydrazine, diborane, ketene dimer, dimethyl suflfate, diphenyl-methane-4, 4 '-diisocyanate, ethyl chloroformate, thio-ethyl chloride, ethyl dichloride EPN, ethyl phosphorus dichloride, dibromoethane, ethyl imines, oxirane, fluorine, formaldehyde, hexachlorocyclopentadiene, hydrogen bromide, hydrogen chloride, hydrogen cyanide, hydrogen fluoride, hydrogen iodide, hydrogen selenide, sulfuretted hydrogen, iron pentacarbonyl, isobutyl chlorocarbonate, isopropyl chloride, isopropyl isocyanate, methylsufonyl chloride, methyl bromide, methyl chloride, methyl chlorosilane, methyl hydrazine, methyl isocyanate, methyl mercaptan, butyl ester chlorine, n-butyl isocyanate, nitric acid, flue gas, nitrogen monoxide, nitrogen dioxide, normal propyl chloride, parathion, cross chloromethyl mercaptan, phosgene, hydrogen phosphide, phosphorous oxychloride, phosphorus pentafluoride, phosphorus trichloride, sec-butyl chloride, seienium hexafluoride, silicon tetrafluoride, antimonous hydride, sulphuric dioxide, sulfuric anhydride, sulfuric acid, chlorosulfuric acid, vikane, tellurium hexafluoride, tert-butyl group isocyanates, tert octyl mercaptan, lead tetraethyl, tetraethyl pyrophosphoric acid, tetramethyl lead, titanium tetrachloride, toluene 2, 4-diisocyanate, toluene 2, 6 diisocyanate, trichloro-acetic chloride, trifluoro-acetyl chloride, tungsten hexafluoride etc.

Another embodiment is a kind of equipment of monitoring radon and α particle.

In another embodiment, the indicator layer in described indication mechanism is arranged on a substrate, and can at random be arranged on the both sides of substrate.

In another embodiment, described indication mechanism is a kind of indicating equipment for different sterilization levels.

It is a kind of a kind of determine reagent concentration method that the present invention also has another embodiment, comprises monitoring by described indicator layer dissolving or is partly dissolved the required time, or monitoring the variation that described indicator layer occurs aspect electric conductivity or opacity.

Be described in more detail the present invention below in conjunction with accompanying drawing and hold the indication mechanism of weighing this.In order to make accompanying drawing more simple and clear, in accompanying drawing, there is no need to mark ratio.For example, in order to seem clearer, the diameter of some parts is than other obviously amplified (an as directed thin metal layer).Although in accompanying drawing and example, metal indicator in described indication mechanism and metal indicator layer 30 can be to be all made up of the various materials with suitable metal performance, but we can be exemplified as a kind of metal, especially aluminium or aluminium lamination are used as a kind of indicator and/or indicator layer.In addition, in accompanying drawing, can repeatedly occur that rightly identical sequence number represents corresponding part.

Fig. 1 is the cut-open view of the indicating equipment of a kind of base current (a) and existing (b).As shown in Fig. 1 (c), most metals has self-assembling formation, the passive oxide layer of protectiveness.The thickness of the oxide skin(coating) of this natural formation is determined by metal, metal purity and other processing.In order to make accompanying drawing clearer, in other figure, do not show the oxide skin(coating) of this natural formation on metal level.Prior art and current equipment are all provided with (1) activator band 1, it comprises a substrate, which is provided with an active agent layer being formed by activator matrix 100 20, wherein in activator matrix, contain a kind of activator 1,000 and (2) indicator strips 2 that are arranged on substrate 40, it comprises a kind of indicator or indicator layer 30.But, current equipment (equipment of the present invention) and indicator strip 2, different completely significantly in feature, composition and the design of indicator layer 30.Indicator layer 30 (nonmetal) in technology requires to be made up of a kind of matrix that contains activator 2,000 200 now, and described matrix can be a kind of binding/resin/ink/pigment or contact adhesive.Indicator layer in existing equipment does not have matrix.Indicator 30 in the present invention, if a kind of metal is that film is shaped.The indicator layer that does not need matrix/binding is by creatively for an a kind of indicating equipment, and becomes the preferred embodiments of the present invention.Indicator layer in equipment does not require a kind of matrix at present.It can directly be used on indicator substrate as one deck/film, and does not need a kind of matrix, and it still can be bonding and changes color or transparency/nontransparent degree like this.Described indicator layer is as a kind of matrix, a kind of indicator and layer thereof.Indicator of the present invention can self carry out bonding, and with its base plate bonding.An embodiment of the indicator layer in described equipment is a kind of metal, as aluminium.When the stealthy salt of one and activator optionally, during as acid, alkali and reactant salt, aluminium can be directly coated on plastic sheeting by vacuum deposition (as evaporated or sputter), and change color or nontransparent degree, as silvery white/opaque, finish reflection and become substantially transparent, colour.Described metallic luster/glossiness is also referred to as reflectance conventionally, changes opacity and is conventionally also referred to as change reflectance.Metal or its alloy are creatively used as a kind of indicator in a kind of indicating equipment, and become the preferred embodiments of the present invention.

In addition, have the oxide skin(coating) of a self-assembling formation on described metal, as shown in Fig. 1 (c), this layer becomes a permeable or separation layer of activator.In the equipment of prior art, need to use infiltration/separation layer.We find in indicating equipment, and the oxide skin(coating) of this self-assembling formation becomes a very important destructible isolation or pervious course, and it especially can increase the time of having reacted.We also can believe that described oxide skin(coating) cannot permeate for most of activators, and therefore great majority may destroy, as a heterogeneous reaction occurs for they.This non-infiltration isolation or layer, transparent, opaque, colour or achromaticity, self-assembling formation or artificially use or manufacture, all can produce an induction period.The separation layer of this self-assembling formation that can be destroyed by a heterogeneous reaction is by creatively for a kind of indicating equipment, and becomes the preferred embodiments of the present invention.The oxide skin(coating) of this self-assembling formation is conventionally thinner than metal level, and in order to make accompanying drawing clearer, other accompanying drawing does not show it.

A thin metal or metal alloy layer, it is with or without metal oxide layer, and is with or without a precursor layer, for example a kind of indicating equipment as shown in Fig. 1 (c).Metal and alloy thereof are known can reacting with most of material/chemicals/reagent.In the time contacting with these chemicals, a thin metal layer both can directly react with these chemicals, also can make a kind of chemicals and described precursor layer react and produce a kind of activator.

Also can not use metal, and use as various in high molecular dye and polydiacetylene etc. as the nonmetallic materials of colored materials and a kind of dye coating of distillation, because they do not need a kind of binding.High molecular dye and polydiacetylene are polymkeric substance, and they are a kind of very thin dye coatings, and what they obtained by processing modes such as distillations also can be very thin, can be thinner than 1 micron.A kind of opaque, there is no binding/matrix, can self bonding and/or self colored thin metal indicator layer by creatively for a kind of indicating equipment, and become the preferred embodiments of the present invention.

Shown in Fig. 2 is that color is with respect to variation (reaction rate, change color degree, change color or the transparency change) figure of time by after equipment activation existing and of the present invention.Change color in equipment is all asymptotic (as shown in Figure 2) conventionally now, asymptotic variation/the change of color is (very rapid when beginning, then slowly slack-off) without any induction period, because described activator is little by little to spread/be distributed in indicator matrix or reaction with it.As shown in Figure 2, in the prior art, the character of a metal level and an activator/chemicals is antipodal (as shown in Figure 2).This substantially contrary character of color/transparency change is by creatively for a kind of indicating equipment and become a preferred embodiment of the present invention.Term distributes and is diffused in herein and can mutually replaces.In existing equipment, reaction is in a kind of matrix, as occurred in indicator matrix.Indicator layer of the present invention does not have matrix, and impermeable.The indicator layer of a non-infiltration is creatively used in an indicator equipment, and becomes a preferred embodiment of the present invention.In addition it also has an oxide skin(coating).Therefore its surface can react substantially.Therefore reaction is heterogeneous.This heterogeneous reaction is to occur on the surface of indicator layer, and activator is not also diffused in indicator layer, and the induction period that therefore makes equipment is by creatively for an indicating equipment, and becomes a preferred embodiment of the present invention.Also can be that activator is diffused at leisure oxide skin(coating) and/or destroys oxide skin(coating) described induction period.Compared with prior art, indicator/dyestuff can be spread in activator matrix really, and activator/metal of the present invention can not be diffused in described activator matrix.The indiffusion of activator in matrix or do not distribute by creatively for a kind of indicating equipment, and become a preferred embodiment of the present invention.Equipment of the present invention only produces very little change color or transparency change in the specific time (as induction period), then can promptly change color, when described metal level is destroyed can become after falling colourless/transparent.Activator destroys the oxide skin(coating) in indicator layer and indicator layer to need the regular hour.Indicator layer and oxide skin(coating) thereof carry out etching reaction/melt/destroy also by creatively for an indicating equipment with a stable speed, and become the preferred embodiments of the present invention.Because metal is the most opaque material, to be therefore left before unreacted at a superthin layer of this metal, it is substantially the same that its color/opacity can keep.If last thin layer is destroyed, so described indicator layer can become transparent.The induction period that the color/opacity thereupon producing changes is by creatively for an indicating equipment, and becomes the preferred embodiments of the present invention.In existing equipment, end points determines that the change color in district is very little (as being less than 5%).In the present invention, end points determines that the transparency change in district can exceed 80% conventionally.This obvious color/transparency that end points is determined district is by creatively for an indicating equipment, and becomes the preferred embodiments of the present invention.End points determines that this color/transparency change rapidly and significantly in district makes equipment of the present invention obviously more accurate than existing equipment.

One has the indicating equipment of long induction period, be similar to (b) shown in Fig. 2, the equipment of a lot of prior aries of also can making a profit, if this equipment have a separation layer or can add an activator or reagent impermeable, thereby with described activator or reagent occur etching heterogeneous/surface reaction, as it is completely as a destroyed separation layer.This method that can breakable layer and utilize one of this layer of preparation long and/or steep induction period is by creatively for an indicating equipment and become the preferred embodiments of the present invention.Described can breakable layer can be organism, inorganics or polymkeric substance.Can breakable layer be preferably a kind of inorganic material, as a kind of metal oxide.

In the prior art, change color normally for illustrate from opaque become transparent.

Fig. 3 is the structural representation of basic layer more of the present invention and optional layer.Also can additionally increase as required described layer.These layers can be random color, shape, thickness, size and character.The relative position of these and other optional layer can change conventionally, and conventionally can exchange.Most of layer is complete, local or noncontinuity.Some layers can be pattern, information or image.Described basic layer comprises the activator band 1 of (1) belt substrate 10, on it, there are an activator matrix 100 and activator 1, the active agent layer 20 of 000 composition, the indicator strip 2 of (2) belt substrates 40, on it, there are an indicator layer 30 and one to stop optionally permeable layer 60 of marker 50 and, (3) by 70, one releasing layer 80 of a contact adhesive (PSA) layer and the storage belts 3 that release pad 90 forms.Described termination marker 50 is stressed, but it is not indispensable.When indicator layer becomes when transparent, described termination marker can become visual layer.Described stop layer 50 also can be arranged between indicator substrate 40 and indicator layer 30.Described pervious course 60 can, for extending the induction period of reaction/transparency change, change the required time of transparency change, changes activation evergy.Described indicator layer has the oxide skin(coating) (not shown) of self-assembling formation, it can be also a self-assembling formation permeable/separation layer.For equipment of the present invention is stored and is applied on an object, described indicator substrate 40 or termination marker 50 can have storage belt 3.Described psa layer 70 can be applied directly on described indicator substrate 40, and described releasing layer 80 can be applied to activator substrate 10 or vice versa.When described activator band 1 is applied on indicator strip 2, described equipment is activated.Remove and discharge pad 90 and releasing layer 80, described equipment just can be applied on an object.Described equipment can be according to design/being provided with multiple additional opaque layers, as opaque top color or Information Level 61, opaque activation indicator layer 62, opaque amendment indicator layer 63 and etching/reaction hood 60 (in Fig. 3, do not show, but Figure 15,23 and 38 having shown).These opaque layers, as top information layer, active layer, amendment marker and prevent that reaction hood layer is by creatively for an indicating equipment, and become the preferred embodiments of the present invention.Described opaque layer 60-69 has extra color, design effect, information, image and instruction.Activator and indicator belt and opaque layer 60-69 can need one or two bonding agent/binding layer, as a PSA is glued together they and adhesive phase.The character of these different layers of equipment of the present invention and transparency are to be decided by the application of equipment.For example, in great majority application, activator and/or indicator substrate are transparent and/or clean plastic sheetings.For example, but in some applications,, as Figure 10, shown in 11,34 and 35, they are opaque, translucent, coloured or have information or have image.An opaque layer can be an amendment marker, also can be arranged on any suitable location of equipment.Can in equipment, add other optional layer, for example one can increase a precursor layer 68 and an etching cover layer 69 (as Figure 15, shown in 23 and 38) and carrys out the indicator layer described in optionally etching.In an equipment, also can there is more than one identical layer, as two metal/indicator layer, and/or two active agent layer.These layers can have their binding.These optional layers can be by a microencapsulated material, as a kind of activator composition.

Described indicator layer many other layers can also be set up and down, these layers can additionally be arranged on the upper and lower of indicator layer in various other modes.An example is a precursor layer 68 being arranged in indicator layer 30.When these precursors and another kind of precursors reaction, activator or reagent can produce another kind of by the activator of dissolving metal.For example, the ammonium nitrate arranging in indicator layer, sodium nitrate or sodium nitrite precursor layer can not affect indicator.When a kind of weak acid of activation, during as phosphoric acid, nitrate can generate nitric acid, and nitrite can generate a relatively strong acid, as nitrous acid or nitric acid, their can than phosphoric acid quickly with indicator reaction.It also can and/or use strong acid and highly basic to be used as activator when dangerous in other difficulty.Therefore, can prepare original or on request a kind of activator that can generate.

Herein term is dissolved for described method, metal as a kind of in etching reaction, thus substantially destroy its metallic character.

As required, application and situation, a hypothallus, as the hypothallus of an active agent layer can have a kind of bonding agent or a non-bonding agent, it even can be applied directly on indicator or other layer.For example, manufacture a biobelt TTI, one can use a kind of bonding agent, as a kind of contact adhesive.But in other application, as a kind of precursor that contains a kind of activator or activator can be applied directly in indicator layer.These non-adhesive stromas can support an activator or activator precursor, and they can be more effective under applicable condition, as in the time reaching certain temperature and humidity level.

As required, application and situation, a kind of activator can be replaced by its precursor.As, in the disinfecting process of oxirane and hydrogen peroxide, one can use precursor, as sodium thiocyanate and tetrabutyl ammonium bromide.After sodium thiocyanate and reacting ethylene oxide, can produce NaOH, it can react with metal level and deposite metal layer.Similarly, tetrabutyl ammonium bromide can with oxidant reaction, produce a kind of acid as known from experience before hydrogen peroxide or its, as hydrogen bromous acid that also can dissolution of metals.

All devices as herein described is all a kind of opaque, and as the white layer in black equipment, therefore all information and image are all visible.

For by one, the belt with PSA stores, because top layer can have a releasing layer and/or discharge pad (not shown), therefore it can be wound around thereon, and is stored before use.

Fig. 4 is that described equipment is in cut-open view (a) and the vertical view (b) of different phase after activation, as 0,1/3,2/3 after activation and time of termination completely.A kind of activator band is used on described indicator strip, when activation equipment, described equipment shows silvery white (in the time using an aluminium thin layer as a kind of indicator), the reflective surface (decomposing schematic representation as shown in Figure 4) of indicator layer 30.Described activator will start the described oxide skin(coating) of reaction/etching (be commonly referred to dissolving herein, or even the inreal dissolving of described metal), the then metal level described in reaction/etching.Or even started when reacting, the color of aluminium lamination can not become too much [three have been reacted as shown in the of 0,1/3,2/3 above accompanying drawing Fig. 4 (b)] yet, until surplus next thin layer unreacted.After all aluminium is etched, can see for one and stop the color of marker 50 [Fig. 4 (a) and 4 (b) two accompanying drawings below therefore, described equipment produces an induction period, although or even described reaction also do not demonstrate and there is an induction period.Although described indicator layer is without any the variation of color, the color of described equipment still can be from silvery white/opaque color that stops marker that becomes, as red or other color arbitrarily, it is by creatively for a kind of indicating equipment, and becomes the preferred embodiments of the present invention.Also can there is induction period other possibility to form required quality or the concentration of activator in etching reaction.Therefore select for stopping marker 50 color of estimating, stop arbitrarily color as green, red, indigo plant or yellow can obtain conventionally.Stopping marker 50 can be a colored plastic film or the colored coating on substrate 40, and can be arranged on the both sides of substrate.In persond eixis equipment, different colored tokens can not using meeting, rally or an exhibition on the same day.

As shown in Figure 5, described termination marker 50 also can be printed to shape, pattern, quantity, information or the image 500 of any expectation.As shown in Figure 6, can replace and select a coloured termination marker can be printed to arbitrary shape, pattern, quantity, picture, image or information 500 or a bar code, therefore an optical scanner, CCD camera or card reader/detecting device can read and point out to reject expired product.Described bar code can pattern, comprises a two-dimentional bar code.Described information can be arbitrarily, as " banning use of ", and " expired ", " danger " etc.Therefore, described equipment can provide a kind of easy method substantially obtain nonrestrictive final/stop color, shape, pattern, picture, image, information etc.Thisly in the time that equipment stops, substantially obtain nonrestrictively, the method for random color or information is by creatively for a kind of indicating equipment, and becomes the preferred embodiments of the present invention.

Shown in Fig. 7 is cut-open view (a) and the vertical view (b) of described equipment, one deck of this equipment is upper and lower or inner is printed on an information 501, or on a surface of activator substrate 10, be printed on this information 501 as a top information, and be provided with another information 502 on upper and lower or the inner or indicator substrate 40 of stop layer 50.At this moment, two information 501 and 502 can be combined into a kind of new final information in the time that equipment stops.A part for final information as " available " is printed on the surface of activator substrate, as shown in Fig. 7 (Ib), can be seen in the vertical view of equipment.These information instruction perishables are available.The reserved area of information, if " non-" is the rear surface that is printed on indicator substrate, as shown in Fig. 7 (2b).This layer/information (" non-" in mirror image) is sightless on vertical view, because this marker is opaque.In the time that this equipment stops, described indicator layer can become transparent, described information " non-" and become visiblely, and in vertical view, it is shown as " banning use of ", as shown in Fig. 7 (3b).Therefore the information after combination " bans use of " and indicates these perishables to use.Therefore,, while using this equipment, do not need to print introduction for user.These equipment are automatically to read/indicate to introduce.Two kinds of information of this combination, the first shows or becomes visiblely in the time of a subsequent stage of equipment, forms a new information, these are by creatively for an indicating equipment, and become the preferred embodiments of the present invention.

In brief, much information and image can combine the final information/image of formation, and for example " bad ", " can not be finished ", " banning use of " produces similar information with " not all right " or mark with image.

Can there is a change color in various systems, normally gradually change, and therefore requires a color reference table.Use method for selective etching of the present invention, can form information, as printed " sterilizing " with the identical isolation ink/bonding agent of color, but can etchedly not affect.Described information can be not clearly.In the time that equipment is processed, as a disinfecting process, can be dry heat or moise-heat sterilization, can there is the variation of transparency in described metallic coating, make information obviously visible.

Some marks, as a check mark (V) mean can (as fresh) and X can be used to indicate acceptable and non-acceptability.

Similar equipment forms a part of bar code or a bar code on described activator substrate, forms remaining bar code or another bar code after indicator substrate.At this moment in the time that equipment stops, two information in conjunction with time can make a new final numbering/bar code or two bar codes all become to can read.The first bar code information can be price, and the second bar code information can be understood as termination, refusal or do not sell.These bar codes can be different size/thickness, can be also different shapes.Bar code also can change coding, pattern, information or image arbitrarily into.

Similar, make the color of information and stop layer identical, just can make an information disappear.

Similar, the final information of a part that is printed on indicator layer upper strata can disappear in the time contacting with a kind of activator, and described equipment stops.

In the above-described embodiments, described information is word and bar code.But described information can be arbitrarily, as pattern and image.Also can form without limitation the combination of information, as word bar code, pattern and image combining are got up.

Indicating equipment of the present invention does not require a kind of coloured reference diagram/line, because simple and easy significant mirror image can disappear as opaque indicator, and the coloured or any information being imprinted on below can become visible.But, coloured reference diagram/line also can increase as requested/print, because equipment of the present invention can change by Show Color, specifically from silver/white mirror image as transparent/colourless in complete-> lead-> light gray-> (or stop the color of instruction, as redness).Therefore,, in order matching with the equipment of current commercialization, can to print coloured reference diagram and illustrate and read/judge described equipment.The equipment of these types can read automatically, and carries out colored coupling.

Fig. 8 is provided with (b) and is not provided with in the indicating equipment of (a) pervious course the structural representation of some basic selective layers.Although the infrastructure device with pervious course can not provide an induction period yet, the selectively suitable pervious course 60 that can apply/be coated on marker 30 makes transparency change required induction period and the time can increase.

Fig. 9 be described also have and equipment activation without a pervious course after, color change (change color or transparency change) is with respect to the expectation variation diagram of time.The length of induction period is determined by many kinds of parameters, comprises performance, perviousness and the thickness of pervious course.As shown in Figure 9, a kind of band is shorter the induction period that equipment thicker and/or more low permeability layer provides than a kind of band the induction period that more equipment of most permeable zone and/or thinner pervious course provides.We find to select suitable condition, and as the thickness of aluminium and pervious course, can increase by 90% or more described induction period.We also find that a thicker aluminium lamination can make transparency change, and make the boundary line of the mobile boundary line equipment shown in Figure 10 steeper.

Because the time that indicator layer is required is very short, therefore described band more the indicating equipment of low permeability layer (as the slow diffusion of activator) will provide longer, a steeper induction period, vice versa.Therefore, this equipment can provide one better " go-do not go) indicating equipment, various indicating equipments especially as herein described are desired, as visitor's pass equal time indicator (TI).

Figure 10 is cut-open view (a) and the vertical view (b) that an indicating equipment with wedge shape pervious course is in the different phase after activation.If described pervious course is even thickness, can there is transparency change in it so within a short time.But if described pervious course is wedge shape, as shown in figure 10, the thin end of pervious course, to thick end, transparency change can occur continuously so, therefore can see between unreacted metal level and coloured termination marker and can produce a boundary line.U.S. Patent No. 5,045,283 disclose this method that forms mobile boundary line by permeate/separation layer of wedge shape, and it can become list of references of the present invention.If described termination marker is printed on numbering, these numberings start the thin end from pervious course to show to thick end so.This boundary line by steeper the diffusion than in existing equipment (as U.S. Patent number: the biobelt as described in 5045283 moves boundary line equipment.Described pervious course material can be any organic or inorganic material, but preferred a kind of polymeric material, especially preferred amorphous polymeric material.In the present invention, also can form a steeper mobile boundary line equipment by a wedge shape indicator layer, because described reaction carries out in equipment surface, and not need matrix.

Similarly, can replace wedge shape continuously by the wedge shape of ladder type.The wedge shape of this ladder type will provide continuous, a staged profile of a numeral or any information.

The material of this wedge shaped layer can be also a destructible separation layer.

Photograph, information, image etc. can also be printed on to the upper and lower of the different layers in equipment shown in Fig. 3, make on this indicating equipment, to show, do not show these photographs, information, image etc., or make them fuzzy, dimmed or thin out.An example is visitor's pass of preparing as shown in figure 11, and produces result as shown in figure 36.A visitor's 501 photograph can be printed (as passed through a kind of printing method/equipment, as laser, ink-jet, heat sublimation etc.) on a transparent indicator substrate 40, this substrate is provided with an indicator layer 30 (as a metal-polyester film), and in this indicator layer, be provided with an optionally pervious course 60, as shown in Figure 11 (a).This structure (indicator strip) can be used on activator band, this activator band is provided with an opaque activator substrate 10 and by the substrate composed active agent layer 20 of activator, and described activator matrix contains a kind of activator (as phosphoric acid) to be prepared visitor and notice card.After equipment activation, described photograph 501 is by the demonstration as shown in Figure 11 (b), because opaque substrate 10 and the described indicator layer of activator band are all opaque, the image therefore showing when the top of the pass will be visible from behind.After the pass stops, described indicator layer is transparent by disappearing/becoming, and because the background color of substrate 10 is colored, and therefore photograph is shown in red/fuzzy, and shows another information, as shown in Figure 11 (c).If activator substrate is transparent, can all see in both sides so photograph.If described activator substrate is to be printed on arbitrarily other information 502 (as the X in this example), so described photograph, by dimmed under red background, and shows " X ", as shown in Figure 11 (c).We have prepared various only have " X ", only have red background, have " X " of red background, and top is just like " termination ", " forbidding " and " effectively " word and have the various device of words such as " no " below.The required time of all these equipment generation transparency change changes according to the thickness of pervious course, character and/or other variable of the present invention.

Figure 12 is provided with the cut-open view of the indicating equipment of various different layers (disconnected property) in diverse location and junction, position.This noncontinuity or continuity layer can be different compositions, shape and size substantially, comprise image, mark, symbol, lines and a grid of different colours or information.If described equipment is a TI, as visitor's pass, so described indicating equipment can be printed on top a photograph 500.Described noncontinuity layer 68 can be below photograph or on indicator layer, as shown in Figure 12 (a) and 12 (b).Described indicator layer self is can right and wrong successional, as shown in Figure 12 (b) and 12 (c).Described noncontinuity layer can be as shown in Figure 12 (d) be imprinted on being imprinted on activator substrate on separation layer and as shown in Figure 12 (e)-12 (h).These discontinuous layers can carry out various combinations.Described equipment can have plural noncontinuity layer.Figure 12 has also shown that the site/position of a layer can exchange.

In Figure 11 and 12, the pervious course of equipment is even thickness.If the pervious course of described equipment is wedge shape, photograph will become colored gradually so.The example of this mobile boundary line concept as shown in figure 36.This equipment will be warned user and remaining time of Security Personnel.Select suitable flaggy, color and opacity can make described image, information and photograph there is different visibility/opacities.Also a photograph or information can be imprinted in described indicator layer.

The said equipment has shown a complete composition of described photograph.Can also partly cover photograph and/or with any direction cover.Similarly, can make any information, as " cancellation ", " termination " etc. are presented on photograph.

Described equipment can be arranged to various.Each equipment can be by various character, shape, size, form, the layer of color and position.For example, one of them can make a prefabricated ID and homologue, or wherein a part is slowly dimmed or thin out, if described indicator layer becomes opaquely or coloured from colourless, or becomes color B from color A.Also having another kind of mode is to cancel/stop a prefabricated ID and homologue, and is covered on the termination image in the biobelt equipment activating.In this equipment, activator band (being provided with an active agent layer on a transparency carrier) is attached on indicator strip (being provided with a wedge shape pervious course on a transparency carrier, an opaque indicator and a psa layer) and can makes described indicating equipment.Then, the indicating equipment after activation is partially covered and sticks an image or photograph.Described activation zone little by little becomes the thin end from belt to thick end transparent, and described stealthy photograph will become visible in time gradually.ID scope or the like device of the indicating equipment after band activation can be directive.As we are in the temporary patent application #61/127 of application on May 14th, 2008, described in 565, the indicating equipment band after this activation can have a feature of amendment indicator, and can become list of references of the present invention.

Image, information, pattern etc. comprise mobile boundary line this unexpected and/or stable demonstration, disappearance, fuzzy, cross out, coloured by creatively for a kind of indicating equipment, and become a preferred embodiment of the present invention.

The described indicator layer being arranged in the said equipment can have different opacities and color.Above-mentioned indicating equipment can have an amendment marker, as described in adhesive phase 70 grades have the silicon coating of a selectivity pattern.If described indicating equipment is modified, as shut down, it will be shown so.Therefore the present invention can become temporal evolution by prefabricated ID and homologue/file, automatically stops, and if need to can also be instruction amendment.

The indicating equipment of these types, as arranged a clamper or the holder equipment as described in fixing on visitor's pass.

Can also be by the described wedge shape of preparation, the indicator that the other end is thinner as one end is thicker and/or active agent layer form the equipment of a mobile boundary line effect and associated.We prepare the various mobile boundary line equipment with wedge shape active agent layer.

Figure 13 is two kinds in multiple band shape of the present invention or foldable device.Wherein activator and indicator strip can adhere to or directly apply/be attached to one with or the diverse location place or the both sides place that open belt base plate.For example, shown in Figure 13, be arranged on band/substrate 15 same side/lip-deep activator band " A " and indicator strip " I ".Described is with 15 can fold around an object (not shown), and as a perishable bag or people's wrist, when as shown in Figure 13 (b), on the indicator strip described in activator band is attached to, this equipment is activated afterwards.Shown in Figure 13 (c) is another example, and wherein said activator band 1 and indicator strip 2 are arranged on on opposite side/surface of 15.Described is with 15 to fold around an object, and as a people's wrist, as shown in Figure 13 (d), after activator band is attached on described indicator strip, described equipment is activated.For the change color that consequent indicating equipment is occurred is visible, it is transparent having a substrate at least, or described activator and/or indicator strip should be the ends that is attached to belt.

Figure 14 is the cut-open view of the possible variation of the another kind of a band shape or collapsible indicating equipment, wherein equipment is provided with a major part of substrate, this part is folding/is activating after (b) front (a) by an indicator layer, as metallo-plastic film hides.This equipment can be prepared simply, as preferably indicator layer being coated in a part for a side half, active agent layer is coated in a part for opposite side half.This zone of reflections can be found simply outside a segment distance, also can in the time stopping, be distinguished simply.

In the equipment shown in Figure 13 and 14 only some band for adhesive tape.If described band is made up of piece of metal plastic sheeting, indicating equipment does not just need an indicator strip so, because this metal level can be used as an indicator.Also can be by an opposite side/surface that has the activator matrix of activator to be attached to belt.This is a kind of embodiment for preparing belt indicating equipment.This belt indicating equipment of being made up of a metallo-plastic film has another advantage.When described metal level is activated after agent dissolving, automatically layering of described belt or thin out, it will automatically become disabled like this.It is aluminum metal layer that this belt can have half, and remaining half is activator/matrix.After described belt is activated, will cover described object, as wrist, and also can see/notice from afar, because the reflective of aluminium lamination.This indicating equipment also can have an amendment indicator.The activator band that can use brown having been applied by selectivity to discharge separation layer is prepared an amendment indicator strip.This discharges separation layer is by a kind of non-sticking lining material, and as silicon is made, this material can prevent the movement of activator.An indicating equipment with this release separation layer can make indicating equipment amendment instruction.

Also activator and activator end of tape can be coupled together and form a belt.They can couple together by various Sealing Method, as with a kind of bonding agent or ultrasonic soldering.

All further features as herein described, as different colours, information, bar code, image etc. also can be combined with belt indicating equipment.

Indicator layer (aluminium) in present device is destroyed in the time of reaction terminating.Bonding destroyed due between indicator substrate and the bonding agent of pervious course (if there is) or active agent layer, therefore described indicating equipment is no longer complete.This is also an advantage in some applications, if wonder in these application that layering stops, as visitor's pass or band.But, other application in, this layering of whole equipment or thin out be unallowed.Therefore, for indicating equipment is connected, this equipment needs a band bonding agent, and as the skin of PSA, this layer is all larger than the other parts of equipment.Also a lot of methods can make described indicating equipment after termination, still keep integrated.For example, activator band set in an indicating equipment is larger than indicator strip, or in the extra band arranging in an indicating equipment, has an adhesive phase (on substrate, having a psa layer).Also having another kind of method is to use a part of metal indicator layer, as metal level point or line, instead of metal level continuously.Described non-metallic part can still connect after equipment stops.One more simply prevents equipment layering, make it to keep integrated method be a polymeric layer is coated on described metal level and/or under, after it is connected with activator, understand bonding more firm than PSA.Can use acid, alkali as tackifier.For example, we find that phosphoric acid is polyvinylether, as a kind of tackifier of polyvinyl ethyl ether.If on metal level or the thin layer of a polyvingl ether of lower use, so just can layering, because after phosphoric acid contacts with polyvingl ether, can make the latter become firmly PSA of one, thereby prevent layering.Also have another kind of method can prevent layering, use a kind of PSA of active agent layer, it is PSA very firmly, and described activator is tackifier or a PSA, it can read aluminium lamination and dissolve after the reaction result of slaine.

In addition we also find in a PSA, and the layering of activator is not a main problem, because described metal level very thin (100 dust), because its dissolving only can be on the very little impact of bonding generation between each layer.The composition of slaine can contribute to keep bonding.

Polystyrene, Polyvinylchloride (PVC) and cellulose acetate use the plastics that can destroy/damage, as also can prepared a kind of amendment indicating equipment.We are in the temporary patent application #61/127 of on May 14th, 2008 application, and the amendment instruction materials and methods of these and other described in 565 can be for the preparation of the instruction of modifying of described indicating equipment.

The heterogeneity that described indicating equipment can be as shown in Figure 3 and the various layers of position or increase as required the distinct methods such as additional layer and form.The first has a cover layer, cover indicator layer while preventing responding layer or etching.These word covers, cover layer, separation layer, prevent that responding layer or etching cover can be used alternatingly in the present invention.An etching cover is a separation layer, and it can obviously prevent activator diffusion by one, and the material that indicator is not destroyed is made.The total area of described etching cover is less than indicator layer.

Figure 15 is a kind of cut-open view and vertical view of indicating equipment, this equipment is provided with the etching cover 69 of an X-shaped in indicator layer 30, when after (1) activation, the equipment after (2) stop and after (3) termination has a colored indicator layer 40 that stops.After described equipment is activated, described etching cover 69 can prevent that activator from spreading, and the activator is here a kind of etchant of aluminium lamination.Described etching cover is preferably made up of a kind of transparent polymeric material.An etching cover that is printed on " X " is set on described indicating equipment, and after this equipment is activated, the trace on described cover can become sightless, and this equipment will be as shown in Figure 15 (1b).After equipment stops, do not have the region of cover/insulation blocking will be etched, become transparent.Because activator/etchant can not be diffused in cover/isolation, therefore cover/isolation under region can keep not etched/do not react, so just can show a pattern [X as shown in Figure 15 (2b)].If described equipment has a colored termination marker, it will be as shown in Figure 15 (3b) so.Also can not print X, and print out of Memory, as word, bar code, pattern and image.Word, bar code, pattern and image are combined and can form the necessary information combination with etching cover.Described etching cover, one prevents that responding layer from being a kind of high impenetrability and the non-destructive layer that can isolate activator.

Use an etching cover, infiltration or impervious formation can make the required time of transparency change grow to the various selections between extremely short from the utmost point.

An etching cover 69 can use in the mode similar to pervious course 60, and the equipment that this pervious course forms also can by with the similar etching of pervious course performance hood-shaped become.The equipment performance that etching cover and pervious course form is substantially similar.Can also stop rear monitoring time mistake at equipment.Described etchant/activator spreads under cover, and starts the indicator layer described in etching.

The preparation person of perishables indicating equipment and other user conventionally because a lot of reasons be unwilling to use very little TTI and other indicating label in the independent unit of perishables or other structure, as the TTI labeling requirement of the suitable size of (1) specific installation and large quality is attached to the correct position of container, (2) be related to independent TTI label, the loss of temperature and obstruction, (3) expense of TTI label and application thereof is very high, (4) client did not accept to understand education/training of TTIs, (5) also relating to product reclaims and rejects, (6) cannot use and can receive " go-do not go " type TTI.

But perishables fabricator may use a TTI on the carton box/box of perishables, because they wish can confirm before perishables are placed on storage shelf that perishables are not with hot method abuse or expired storage.In addition, existing TTI is too little, and therefore on big box, it is difficult in sight.Box normally seals with a kind of pressure sensitive sealant band.And box also has large label to identify product and manufacturer.If described band or label are TTIs, perishables manufacturer/retail trader is used band TTIs possibly on each box, because (1) do not need the TTI label of the suitable size of special equipment and large quality, (2) do not worry that client gets rid of independent TTI label or revise, (3) each unit cost of such band TTI label is very low, (4) client does not need to accept the education/train, (5) because TTI equipment disclosed by the invention can read or marked change automatically, because it is that application that can contact and (6) label and band is without any need for extra manpower.Described band and label TTI can be for identical objects, except under the low expense being necessary.

The invention provides a kind of possibility and prepare band and label TTI.Activator and indicator strip are cut apart and are applied on a perishables box by a biobelt/two band dispenser, seal described box, also can automatically monitor.People open box, can find simply whether these perishables in box are superior in quality or expired.

TTI band of the present invention carrys out sealed box without any need for special equipment.Use TTI band can not make cost be increased to the level that perishables manufacturer/retail trader is not used.They wish to know before product is added that product is that matter is measured.Instruct employee, instead of client puts on shelf by perishables very simple.TTI of the present invention does not need the formal training will be very obvious, and can automatically read.

Tape dispensers is known.A kind of tape dispensers is made up of a system that can keep and cut apart a monovolume belt conventionally.Biobelt dispenser of the present invention is a dispenser of supporting two volumes (activator and indicator volume), and the physical construction of their laminate/activators, cuts apart lamination/activation zone with the length of being scheduled to.Drive and automatic labeling label system can be discounted activator in technology and biobelt label/gummed paper of indicator label, this system by AVERY DENNISON's development for cutting apart independent TTI label.But this system can be peeled the label of indicator mark and activator band off, they are aimed at and are attached on a container.Dispenser of the present invention does not need to peel label, because without any many other characteristics of label and little label.

Figure 16 is the cut-open view in the basic biobelt dispenser that the belt after activation with some foundation characteristics is cut apart.Described dispenser 300 is made up of a frame system (framed structure) with glue chain (not shown) door, it can be opened and pack reel into, then close, the handle of a pistol type handle 320 or base are fixed on dispenser on a product line.Also comprise described dispenser wheel shaft and tension force control (not shown) support respectively indicator and activator reel/be with 302 and 312, cylinder 304 and 314, the cutter/partition tools 330 of releasing layer (if there is), laminated web 303 and 313, guiding reel 350, segmentation band etc. is fixed on the correct position place in framework by they.The tape drum of described dispenser on can drive, especially line.The dispenser of described drive can have engine, sensor, and as selective sensor and a computing machine (CPU), the operation of they and tape dispensers and tape dispensers matches.

A small-sized hand-operated dispenser can be used by little user, as at home, and in hotel, victualler etc.

Those of ordinary skill in the art can change according to above-mentioned band dispenser size, material, effect, operation, composition and the use of dispenser.

Figure 17 has been sealed by a tape dispensers from one, and with the box 360 of indicating equipment after activation, as the structural representation of perishables is housed.

In order to seal a perishables box 360, as shown in 17, user promote lamination/traction of band of activation, and be attached on an object, as a box, then promote dispenser or mobile box, and cut predetermined length.

Figure 18 is by the structural representation of a box of indicating equipment (a) sealing after a kind of activation, its on an indicator strip 2 and the termination of indicating equipment (b) be provided with an activator band.On described indicator strip, do not need to arrange a bonding agent.Indicator can be less than activator band.

Also can seal a box with the indicating equipment after an activation, this indicating equipment is provided with an indicator strip that strides across activator band.

Described activator and the size of indicator strip are not identical.A belt can be less or wider than another.Preferably a belt is narrower than another.Described object can seal the box with TTI after an activation.According to design, after indicator strip and activator band pack dispenser into, can make activator band stride across indicator strip, vice versa.Cross after date when the term of life of perishables, described indicator strip is transparent by becoming, and the information and the color that are hidden in below will become visible.

A box can be sealed by a large label type indicator strip, and is activated by an activator band.

Described band and label can have the feature of a lot of previously described other indicating equipments of the present invention, and for example, other basis and selective layer obtain mobile boundary line, bar code, numbering, pattern, color, image and information.

According to these belts and sealed box, less belt can have or not have a kind of bonding agent.One or two band can be modified instruction.

Band after described activation can only be attached in sealer/closure, also can be attached on whole box, or even across on the activation band posting in advance.

Can paste a band (as activator band) with a dispenser, be with (indicator strip) and paste another with another dispenser.This has two kinds of situations, and the one, use indicator strip, another is to use activator band.

System of the present invention makes perishables manufacturer, and storehouse management person and administrator can rotate the box of perishables rightly, thereby reduces the waste of food.

If a perishables bag is made up of metallo-plastic film, described equipment can stick an activator band.

Except using sealing TTI to bring sealed box, described band can be also label, also can be attached on box.Can also be attached on box prefabricated indicator strip as label, when packing into after perishables, stick a kind of activator and bring activation tag.

Maybe can not move if this active agent layer is substantially motionless, as a polyacid layer (polyacrylic acid) or polyamine layer (as polyethyleneimine) and a thin indicator layer (as a pH dyestuff) etc. can move, and react with motionless active agent layer, so also can form all the said equipments and method.

Described band indicating equipment, if by the equipment that activates in advance and store, they still need to be used.This can be avoided the needs to biobelt dispenser.So independent dispenser is used.

Can prepare band indicating equipment with diverse ways.Band indicating equipment can have all features of TI and TTI.Shown in Figure 19-22 is the different preparation methods' of band of the present invention and other indicating equipment cut-open view.Figure 19 is the cut-open view of an instruction/band of some preferred features of a kind of TTI of having, and this belt is to be arranged on for different objects on a substrate, and the same side of this substrate is provided with active agent layer and conventional PAS layer.Figure 19-22 also illustrate as indicator layer 30, indicator substrate 40, stop layer 50, pervious course 60, diverse location, shape, color, the information of the different layers that psa layer 60 grades are glued together an object and Information Level 61.Similar, Figure 20 is the cut-open view of an instruction/band of some preferred features of a kind of TTI of having, this belt is to be arranged on for different objects on a traditional band.Although there is several different methods can prepare band indicating equipment, Figure 21 still illustrates some more economical methods.

Figure 21 is that one is arranged on a substrate 10, has the cut-open view of the band of some preferred features of TTI, and wherein substrate is provided with traditional bonding coat 70 and activator bonding coat 20.Whole continuity band must be with as TTI.Figure 22 is a kind of being arranged on a conventional band, have a pair of feature of TTI a band analyse and observe (a) vertical view and (b) cut-open view.

Also can be by preparing aseptic indicating equipment with activator precursor, as oxirane and hydrogen peroxide.For example, when using sodium thiocyanate as a kind of precursor, just can prepare activator agent, as NaOH contacts with oxirane.NaOH is because produced, and etching indicator, thin aluminium lamination or other microparticle.Similarly, if use a kind of precursor, as tetrabutyl ammonium bromide, after it contacts with hydrogen peroxide or its plasma, just can prepare a kind of acid, as hydrobromic acid.Described acid meeting etching aluminium thin layer or its microparticle.Hydrogen peroxide self can etching aluminium lamination.

Use stop a by force/separation layer, it is printed on some circuit, can prevent significantly the diffusion of etchant/activator, can not only form like this information, and can not form a circuit, EAS and RFID equipment.Figure 23 illustrates and forms these equipment, as the vertical view of RDID different step.Electronic component, as a microchip 150 can adhere to/weld 151 correct positions at indicator/metal level 30, as shown in Figure 23 (a)-23 (c).Electronics can be connected with circuit or antenna by conductive paint or welding without part.Described microchip 151 is inertia (a kind of short circuits), therefore can not be read.So a kind of antenna 69 shape isolation/cover materials are printed on metal level, as shown in Figure 23 (d).Then an activator band is attached on whole metal level, as shown in Figure 23 (e).Described activator, by etch metal layers, leaves the not etching region of the lower antenna-like of cover, chip and antenna is coupled together, as shown in Figure 23 (f).Antenna that this method is made or circuit are as shown in figure 38.

Also have a lot of other methods to prepare a kind of RFID indicating equipment and other similar devices, as RFID antenna, printed circuit board (PCB), EAS (electronic goods alarm system for guarding against theft) equipment and conventionally type.For example, can use antenna pattern activator band or print these activator patterns.So form the antenna of a RFID and like device and circuit come monitoring time, time m-humidity, sterilization etc.

The RFID being made up of an electronic chip 402 and antenna 401 shown in Figure 24 embeds 410, and it is provided with (a) and is not provided with (b) activator band 20 and posts an activator band (c) at the diverse location place of antenna 401.In figure, only show the center section of antenna.A RFID equipment is provided with two RFID and embeds, and one is provided with, and another is not provided with an activator band, as shown in Figure 24 (d).Described activator is with the activator of enough quality, the part antenna under its etching base.According to activator band residing position on antenna, the ability that described embedding/chip received and transmitted RF signal can weaken.

Shown in Figure 25 is that RFID in Figure 24 is embedded in the structural representation being activated after agent band etching part antenna.If activator band appropriateness, near of RFID chip or its, as shown in Figure 24 (c), is pasted one of activator band most preferably position, RFID chip is understood completely and antenna disconnects, as shown in Figure 25 (c), it is lost activity and effect, not can read.At this moment antenna is an indicator.Therefore, after the activator band of an energy etching antenna is attached on antenna, described embedding becomes an indicating equipment, as a TTI.If carry out suitable design and use, just can make RFID equipment lose activity, in the time that the inclusions in box is expired.

Figure 26 is (a) a kind of dual damascene RFID indicating equipment 410, (b) has the activator band 1 using in RFID embeds and the cut-open view that (c) not can read (inactivation or disconnection) after activator band 1 etching antenna produces embedding.Described equipment 410 has two RFID to embed, and each has oneself antenna 401 and an electronic chip 402.Described equipment only sticks activator band 1 in an embedding, is then activated, as shown in Figure 26 (b).The antenna of activator band will inactivation, and becomes and not can read, when antenna or a part of antenna etched after.

Unprotected and those RFID that scribble an active agent layer embed also can be for many miscellaneous equipments of the present invention, comprise monitoring sterilization, as moise-heat sterilization.Steam and hot water can dissolved aluminums.If described antenna is made up of a kind of aluminium alloy, because aluminium alloy is more responsive to water, therefore RFID inactivation quickly.In order to use a kind of two RFID monitoring sterilization, a kind of antenna need to be protected by a protective seam, as a water-proof protection cover.

Described RFID equipment can be activated before or after being attached on an object.

Also can use ultra micro metallic particles, the indicating equipment as described in aluminium and alloy preparation thereof, as TI, TTI and SI.At this moment the potpourri that the activator of metallic particles and a kind of ink form mixes can be coated on a substrate.The indicating equipment of making thus has a protective seam or pervious course, and has all further features of TTI of the present invention and indicating equipment.The activator that requires TI or TTI and high temperature TTI or xeothermic indicating equipment is had higher corrosivity and/or concentration by this indicating equipment.This indicating equipment is more suitable for xeothermic or moise-heat sterilization indicating equipment.

Figure 27 is the ink coating 9 of (a) a kind of metallic particles 31 and a kind of binding 100, (b) metallic particles and a kind of activator 1000, (c) the activator generation partial reaction on metallic particles and cut-open view that (d) metallic particles is destroyed completely.Do not need complete dissolution of metals particle.For a special metal, ultrafine particle can dissolve quickly.Metallic particles can arbitrary shape, can have self-assembling formation (as oxide) layer and/or a coating for the protection of property.

Equipment shown in Figure 27 also can comprise the indicator of a metal cation.In the time that a kind of metal and a kind of activator react, will produce a kind of metal cation/salt.Consequent metal cation can with a kind of indicator reaction, produce color and final color in the middle of of indicator.When a kind of activator, as phosphoric acid and a kind of metal, during as reactive aluminum, it will produce a kind of slaine, as aluminum phosphate.Can add a kind of indicator reacting with the kation (as Al+3) of aluminium to monitor or find this reaction.

With the particle of a super thin metal coating, as a thin copper layer on iron particle can utilize, for example in copper solution, precipitated iron particle obtains, these particles also can be used, and be preferably used for indicating equipment transparency change, as sterilization (as steam, oxirane, plasma etc.).These metallic coating particles will occur similarly to change with metallo-plastic film, as scribble on the substrate particle in hole, and copper coating particle can become from redness the color of substrate particle.Many other distinct methods also can obtain shallow layer.

For described indicating equipment can be used on request, can utilize micro-capsule activator and/or indicator.Shown in Figure 28 is method [Figure 28 (a)-28 (c)] and different times [Figure 28 (d)-28 (the f)] structural representation of this equipment after activation of preparation a kind of thermoplastic activable indicating equipment, and this equipment has a thermoplastic being arranged on metal level and can activate and pack into the active agent layer of micro-capsule.Described equipment can be applied a micro-capsule activator 201 (as phosphoric acid or its solution) and prepares, and on a metal level 30 of substrate 40, heating or pressurization just can be broken this micro-capsule [as shown in Figure 28 (a) and 28 (b)].Described equipment also has other layer, is arranged on below and with an adhesive phase (not shown) that discharges straight line as one.As shown in Figure 28 (c), the coating 101 of a protectiveness can also be set on micro-capsule.Use a thermal printer, can print an information or image (or with a hard thing/pen write), as shown in Figure 28 (d).Described micro-capsule breaks 202, and discharges activator/phosphoric acid.An image will show.Described equipment can be removed release wire from behind, is then used on an object or person body.Activator/the phosphoric acid of described release is by the metal level described in etching 203, as shown in Figure 28 (e).In the time of the complete etching 204 of metal quilt, described printed information and/or the color being printed on below will show, as shown in Figure 28 (f).Various device disclosed by the invention and homologue thereof can be as, have layer of different nature, use additional layer, change the position of these layers.

Figure 29 is the structural representation of the activable indicating equipment of a kind of thermoplastic, as shown in Figure 29 (a), a metal level 30 at its base plate 40 1 side places is provided with a thermoplastic can activate micro-capsule activator 201, its base plate opposite side place is provided with traditional hot stamping layer 2001, as Figure 29 (b) start after the activation that is shown in to show and [as Figure 29 (c) and (d)] as shown in termination time.A thermoplastic can be used in to the plastic side of metallo-plastic film by active layer 2001, and micro-capsule active agent layer 201 is used on metal level 30 and prepares Figure 29

(a) equipment shown in.The information of design can be printed on the both sides [Figure 29 (b)] of equipment.In the time that an information 501 (as fresh) only can be seen in top.In the time of activation, described activator is by the metal level described in etching.In the time stopping, the described information 502 being printed on metal (if not) can be seen from top, can also see whole information (stale) as shown in Figure 29 (c).If a kind of color is also to estimate in the time stopping [Figure 29 (d)], a suitable color layers just can be used in the back so.

Can prepare the activable indicating equipment of thermoplastic with diverse ways.For example, a persond eixis equipment can be prepared by the method shown in Figure 30 as visitor's pass.This equipment can be by by one, the contact adhesive containing a kind of activator 20 (as phosphoric acid) be used on the metal level 30 of half, and thermoplastic can active layer 200 be used on a substrate 40 as shown in [as Figure 30 (a)].A release wire 80 is used in described active agent layer 20 [Figure 30 (b)].Activator 20 will dissolve metal level 30 below, makes the activator part of metallo-plastic film become transparent [Figure 30 (b)].Information 500 (being terminated or having a visitor's image during as application) can be imprinted on substrate 40 after, and substrate be provided with a thermoplastic can active layer 2001[Figure 30 (c)].The described release wire starting from active agent layer 80 is removed, and has folded equipment [Figure 30 (d)] in the middle of equipment.Described information 500 is tops of equipment after activation.In the time that equipment stops (metal level is dissolved), a coloured and/or printed information, as redness, " X ", meetings such as " forbiddings " shows [Figure 30 (e)] under information/photograph.

Shown in Figure 31 is to use distinct methods activator, indicator and a kind of adjuvant that can use to be packed into the cut-open view of the example of micro-capsule on marker.Described metal level only can have activator 201 microcapsule layers [Figure 31 (a)], a micro-capsule activator and material 211[Figure 31 (b) that directly thermoplastic can print], a micro-capsule activator and material 211 and a kind of adjuvant 212[Figure 31 (c) that directly thermoplastic can print], micro-capsule activator, directly thermoplastic can printed material material and a kind of mixolimnion [Figure 31 (e)] of adjuvant, the mixolimnion [Figure 31 (f)] of micro-capsule activator and the material that directly thermoplastic can print.In the time that metallic particles is used as a kind of activator, just do not need a metal level 30.At this moment, these layers on substrate 40 just have metallic particles or are mixed with other capsule material.

Also have some other method to make a kind of indicating equipment can use a microcapsule layer.Use a microcapsule layer, the example of preparing an indicating equipment as an activator band (has the substrate of micro-capsule activator coating) shown in figure 32.As shown in Figure 32 (a1) and 32 (b1), on embedding, a RFID can use a kind of activator.As shown in Figure 32 (a2) and 32 (b2), can activate this equipment after breaking micro-capsule.As shown in Figure 32 (a3) and 32 (b3), the activator energy etching antenna after release, and the RFID that makes to can read becomes and not can read.Similar many other indicating equipments also can be produced.

A TTI equipment shown in Figure 33 can show an information " fresh " within induction period, after finishing induction period, can show " cannot ensure " and a bar code (seeing the explanation of embodiment 7 to this indicating equipment).

Shown in Figure 34 is anneal at the 55 DEG C structural representation of different time of a mobile boundary line indicating equipment, and it has the infiltration isolated antennas of a wedge shape.(seeing the explanation of embodiment 8 to this indicating equipment)

Shown in Figure 35 be when activation (a) and termination time (b), the box being sealed by an indicating sealing band.(seeing the explanation of embodiment 10 to this indicating equipment)

Shown in Figure 36 is the visitor's pass of different time of annealing at 55 DEG C, and it is provided with the pervious course of a wedge shape between indicator layer and active agent layer.(seeing the explanation of embodiment 11 to this indicating equipment)

Shown in Figure 37 is that the RFID indicating equipment of annealing at 25 DEG C after an activation of different time embeds.(seeing the explanation of embodiment 15 to this indicating equipment)

Shown in Figure 38 is on indicator (a), to be printed on an antenna, and has at room temperature stored two-piece type (egative film the is down) metallized polymer film of 3 days (b).(seeing the explanation of embodiment 16-B to this indicating equipment)

Figure 39 be a kind of indicating equipment at 25 DEG C, transparency number percent time history plot.As shown in the figure, this equipment has a very long induction period.(seeing the explanation of embodiment 17 to this indicating equipment)

Figure 40 is the instance graph of a moise-heat sterilization indicating equipment, and wherein said equipment is to make (seeing the explanation of embodiment 26 to this indicating equipment) by the sodium acetate of a kind of aluminium (powder) ink of processing under different condition and various concentration.The sodium acetate that aluminium ink composition contains various quantity, it is applied on a transparent mylar, is then dried.A kind of activator is made, and described aluminium powder and activator were all processed under different conditions for sterilization.Divesting of coating can be processed under different condition.As shown in figure 40, described equipment only changes color (becoming transparent) under suitable conditions for sterilization, and under other condition, can not change color.

Figure 41 is the instance graph of the moise-heat sterilization indicating equipment of a mobile isolation, and wherein said equipment is to have sterilized the different time at 120 DEG C.The mobility in (seeing the explanation of embodiment 27 to this indicating equipment) boundary line can be controlled by different parameters, as character and the thickness of infiltration wedge shaped layer and activator.The perviousness of a layer of polyurethane is higher than the perviousness of a polyacrylic acid layer.

Figure 42 is the instance graph of a hydrogen oxide sterilization indicating equipment, and wherein said equipment is to make (seeing the explanation of embodiment 28 to this indicating equipment) by a kind of aluminium ink and the tetrabutyl ammonium bromide processed in different condition.Most preferably hydrogen peroxide of described equipment.Described equipment can be monitored hydrogen peroxide plasma in disinfecting process.Tetrabutyl ammonium bromide and other bromide, as potassium bromide, most probable produces hydrobromic acid, its energy etching metal particle, thus optionally produce hydrogen bromide.

Figure 43 is the instance graph of an oxirane disinfection indicating equipment, and wherein said equipment is to make (seeing the explanation of embodiment 29 to this indicating equipment) by aluminium ink and the sodium thiocyanate processed in different condition.Activator, as sodium thiocyanate, in the time of it and reacting ethylene oxide, most probable produces NaOH.NaOH meeting etching metal particle, becomes this equipment transparent.

Figure 44 is that phosphoric acid makes a kind of aluminium lamination of thick approximately 125 dusts start to become almost transparent, and along with the variation of concentration becomes transparent curve map (seeing the explanation of embodiment 33 to this indicating equipment) completely.

Also can on indicator/metal level, base plate or an object, form more than one indicating equipment.For example, can use (1) temperature and time-temperature, (2) temperature, Time-temperature and radiation, (3) freeze and dissolve and the activator band of Time-temperature indicating equipment Time-temperature and (4).They are designed to can be at the same time or when different time or use under different condition.

In an indicator substrate example of the present invention, it only has a side to be provided with a metal level, and similarly on activator substrate is implemented, only in a side, is provided with an active agent layer.But, in multiple embodiment, as preparation EAS equipment, can use an indicator substrate, its both sides are equipped with metallic coating, and the thickness of these metallic coatings can be identical, also can be different, and metal or metal alloy wherein can be also identical, can be also different.Similar, can also use a kind of activator substrate, there is activator coating its both sides, and a side be provided with layering/metal indicator of activation.Described activator coating thickness can be identical, also can be different, and activator also can be identical, also can be different.Can also prepare described equipment, its active agent layer is to be clipped between two metal levels, and an indicator/metal level is to be clipped between two active agent layer.

Also can prepare a kind of multiple layer equipment, permeate substrate 2/ Information Level 2 etc. as metal level 1/ permeates substrate 1/ Information Level 1/ metal level 2/.

One or more layers, the top layer of especially described equipment can be permeable or opaque, a kind of like this activator, reagent or their gas phase can be passed through.This opaque or permeable layer of (not shown) can be selected part activator, and therefore this only can make the activator of that activator or similar kind pass through.Can use fibrous paper, cloth, synthetic paper and selectivity composition.This is opaque/and optionally layer can be transparent or opaque.

Because described equipment has a very thin aluminium lamination, the information of promotion can similarly write on a CD (CD) or reading manner and the similar equipment of CD.Therefore, each equipment can have ID and the information of self.

Although do not need, for additional safety practice and information, also can be on equipment or print in the side edge of equipment, for example how to use, illustrate, warn, attention, ID, color reference figure etc.

Equipment of the present invention can turn around by suitable variation.

All these equipment of the present invention also can be according to us in the temporary patent application #61/127 of application on May 14th, 2008, and the materials and methods described in 565 is prepared amendment instruction.For example, described indicating equipment can have one or more amendment indicator layer or be made up of amendment instruction material.If described equipment is modified or whole equipment is destroyed, will show so an information, as engineering noise or " infringement ".

As described in many indicating equipments of the present invention, this equipment has two pressure sensitive adhesive layers, and one contains activator, and another can be for a substrate, can be also to make every layer to use amendment or invalid indicator.

All devices of the present invention has one or more layers.Although not explanation, being every layer has two surfaces, and these two surfaces can be continuous, can be also discontinuous, can be also even or inhomogeneous, or smooth or rough.These layers or mark also can printing images, information etc.

Visible remarkable instruction can comprise hiding mark, they are sightless at first, then can become as seen or significantly, and initial obviously then to become sightless mark be that hide or visible, significantly or under different condition, as can be read by machinery under UV light.

Described activator, indicator and described equipment can be any conventional shape and size substantially, comprises ink, pigment, crayon and gel.They can be also pen, inhalator jar and rod shape.Described indicator layer can be a very thin layer, as by vacuum evaporation or ink/pigment coated being prepared from metal micro particles.

Some indicating equipments can be made like this, the potpourri that dissolves of a kind of activator and a kind of binding forms an activator coating, this coating is arranged on an indicator surface, and cooling mixture therefore produces a very little effect in indicator layer rapidly.Similar, described indicating equipment can be made like this, uses a kind of potpourri that dissolves binding and metal micro particles containing activator, preferably prepare respectively, mix rapidly, potpourri is coated on a substrate, cooling rapidly, be glued together with a crosslinked or radiation.

Reflective light source and mirror can cause than other object our attention conventionally quickly.Due to the reflectivity very high (similar with mirror) of aluminum coating, therefore use a kind of metallo-plastic film can cause our attention as a kind of indicating equipment of indicator, and can be noticed simply.But metallo-plastic film is conventionally very flat.They carry out reflected light according to the shape of indicating equipment and angle of light degree.This indicating equipment with planar metal surface only can be noted according to the special angle of light source, indicating equipment and observer's location positioning.If the surface of indicator is concavo-convex equably, these concavo-convex can be reflective in all directions, therefore it can be noted arbitrarily angled simply.For example, a salient point, if any a taper shape, wavy or pyramidal metallo-plastic film can be reflective in all directions, the indicating equipment of institute's art can be noted simply.These films are more preferably for described indicating equipment.Similarly, also can use with the metallo-plastic film of hologram, it can be noted simply, and can be for security.Because this equipment has a reflective surface, therefore it also can be read in the evening of the low light level.

Can also form different types of sterilization indicating equipment.And can be by mobile boundary line equipment as multiple indicating equipment.

In fact we proved invention can use a kind of material, equipment and method improve the performance of some existing indicating equipments (described herein or do not state), utilize many diverse ways, for example 1) with a thin metal layer or metal micro particles replace they coloured/change material, as dyestuff, pigment or other reactants (being so-called existing indicator), these materials various activator/precursors described by the present invention affect, 2) when activator of the present invention can be for thin metal layer of etching or metal micro particles, with 3) by using a destructible isolation or pervious course.The present invention can optimize this two kinds of technology in conjunction with composition of the prior art, method and apparatus.

Above-mentioned and other content of the present invention be can change, some common examples of change, amendment and selection material, equipment and method.By displacement-combination, probably there are a very large variation, amendment and selection equipment and method, for example, by changing the attribute of assembly, the position of layer, the diversity of a layer, increases an extra layer, changes color, the reflectivity of opacity and a layer, increase images/information, by the different size and shapes of a layer or equipment, the various performances of material, concept is used to existing equipment, use other parameter of the present invention.

prior art and comparison of the present invention

Indicating equipment of the present invention is similar with method with other similar devices to biobelt of the prior art at first view.But equipment of the present invention is not only obviously different, and its novelty, creativeness be all exclusive, has many places different from equipment of the prior art, and therefore design characteristics and many advantages of maximum existing equipment can be provided.Some novelties and the creative feature of present device can not design in the equipment of prior art.

Between existing equipment and present device, only there are some common similar features.For example, equipment existing and of the present invention has an activator band, and it is made up of a substrate with activator matrix.These two kinds of equipment have an indicator substrate and one to use the accessory of pervious course, and they can produce induction period of an expectation.Method is below also identical: the described activator band of (1) preparation, as by a coating with activator is coated on an activator substrate and (2) activation as described in equipment, as by activator band is used on indicator strip.This is all significantly similar while end with process between prior art and present device.

Some dyestuffs and pigment, can be in existing equipment according to activator.Described pigment and dyestuff can change color, but can be not destroyed.A very thin metallic coating, a kind of indicator can be used as in the present invention as aluminium lamination uses.Described metal level is completely irreversibly destroyed in the time that reaction finishes.Described metal level can not be regenerated.In existing equipment, change color can reverse, and changes pH as passed through.

In prior art, the thickness of coloured/indicator layer is generally 2.5-50 micron.For example, as the U.S. Patent No. 5,930 of this application such as grade of person of outstanding talent, described in 206, the thinnest indicator coating in a persond eixis equipment is the ink point of-2.5 microns and an opaque layer of-12 microns.In the U.S. Patent No. 7,294,379 of the application such as island, indicator bed thickness 2-20gsm in a kind of folding biobelt equipment (gram every square metre), as 2.5-50 micron thick.

Aluminum layer thickness in present device is only 0.0001-0.0005mil (15-150 dust) conventionally, and 1,000 times of being approximately in existing equipment shallow layer are thick, and it can provide the highest opacity as metal, forms the most opaque substrate.Under 2 selectivity density (average thickness is-100 dusts), metal-polyester piece-99% (the Si Kaite industry of surround lighting, Fig. 2 .3a of bracket I II, Eldridge M edits, the alloying technology reference of AIMCAL metal association, the 3rd edition, Industrial Metal, coating and aluminium association, May calendar year 2001).When indicator coating be about 1,000 times thick, required activator quality also will significantly reduce.

Reaction product is as normally opaque in aluminum phosphate.But due to thickness (100 dust), described layer is normally transparent.

In the present invention, the concentration of indicator/metal level is 100%.In existing equipment, indicator/dyestuff/color depth is less than 5% conventionally.For example, in the U.S. Patent No. 7,294,379 of the applications such as island, the indicating dye quality check concentration of a biobelt equipment is about 0.4%-2%.

Most metals and alloy thereof form a protective seam, are generally an oxide skin(coating), and it can protect their terminal surface, makes it can further not be oxidized.The oxide skin(coating) of this natural formation, as isolation or the pervious course of an activator, therefore can be incured loss through delay effect.In the prior art, need to use an isolation/pervious course.Described protective finish can be formed naturally, and comprises except oxide, as carbonate, sulfate and halogenide or for the protection of metal or its alloy.

Indicator strip of the prior art is by by a matrix for polymkeric substance normally, and the indicator that this matrix contains a kind of normally a kind of dyestuff or a kind of pigment, is coated on an indicator substrate.An important and unique difference is that indicator strip of the present invention does not have a kind of matrix, does not also need this matrix.Indicator strip of the present invention is by an indicator layer is directly used on a substrate, as by a metal level is deposited on a plastic sheeting and is made.

In order to produce the induction period of a change color by time requirement, existing equipment need to add a kind of neutralizing agent in indicator layer.The present invention neither needs a kind of neutralizing agent can not to be added in described indicator layer and produces induction period.Described indicator layer self can produce and make a kind of induction period reaction only occur on indicator surface.

Indicator layer of the present invention approaches 100% opacity.Its below anything all be cannot see.After metal level is destroyed, described indicator layer becomes transparent substantially.Any color, design, image and the information that are imprinted on below metal level all become visible.The termination of this meeting indicating equipment.Not open basic material, layer and the method that obtains non-limiting color, design, image and information of existing equipment.Can utilize simple method, as by any color, design, image and information, comprise that bar code, numeral and photograph, a mark are imprinted on below metal level of the present invention, substantially obtain described color, design, image and information, comprise bar code, numeral and a photograph, mark.

Change color in existing equipment is progressively nonlinear (rapid when beginning, slow when end).Can there is the variation of transparency in indicator layer of the present invention, and this variation is very unexpected as shown in Fig. 2 and 9, as shown in Figure 33 and 39, is antipodal.

Existing equipment needs a color reference figure to indicate termination, because they are not genuine end point.Equipment of the present invention has a genuine end point.Existing equipment does not need a mark on equipment to explain how to go to read yet or account for color changes.This is because the change color of reporting in business machine and in prior art is not significant, and variation opaque from colourless/transparent-> or that vice versa always can occur.Equipment of the present invention is without any need for color reference figure.They can read automatically, automatically stop and explanation automatically.Therefore, equipment of the present invention is outstanding and unique providing aspect required transparency, and information seldom can further illustrate.They also provide want most go/do not go type information, as shown in Fig. 5-7 and shown in Figure 33-36.

The U.S. Patent No. 3,999,946 of Pa Teer etc. discloses a kind of TTI equipment, and it is based on a kind of diacetylene that has an induction period in polymerization (just poisonous 2,4-hexadiine-1,6-glycol-bis--p-toluenesulfonic acid) solid-state polymerization.In other existing equipment, need a pervious course or a kind of neutralizing agent the induction period of the activator in its indicator matrix.The present invention oneself has an induction period, and need not use a pervious course or a kind of neutralizing agent.Metal level information was below sightless before metal level is destroyed, and therefore equipment of the present invention can provide an induction period.This just makes equipment of the present invention be more suitable for monitoring the operating period.

Because reaction of the prior art is asymptotic, therefore the termination time of existing equipment conventionally uncertain, be approximately+20%.The termination time of present device is normally uncertain, is greater than 5%, if use thicker metallic coating, can be greater than so a part of number percent (for example, seeing embodiment 33 and Figure 44).In the time determining the terminating point of equipment or stop, described reaction is conventionally the slowest, for example, see on Fig. 2 chart to be existing equipment institute target " terminating point is determined district ".When worth Note Rate maximizes, and this maximized change occurs in the time that the present invention stops, and sees that the chart upper mark in Fig. 2 is " terminating point is determined district ".

Because conductivity expectation meeting becomes 10～6S/em from 106, therefore these equipment will be high responsive.

The asymptotic reaction of existing equipment can continue a very long time (being eternal in theory), or even after being called equipment termination.Described reaction stops (100%) completely in equipment of the present invention.

Environmentally safe high stability metal with the aluminium of protective oxide layer.Metallo-plastic film, especially those have being widely used of an aluminium lamination, and under home, stablize some years.Therefore, the indicator strip of being made up of metallo-plastic film is environmentally safe stable, and can store the several years.This just makes equipment of the present invention can prevent amendment or amendment is minimized, and similarly provides false mark.The containers labels of described band indicator label (as metallo-plastic film) or time ticket can by prefabricated, store for a long time, or even after being applied on container.Then when container is full of after perishables, use activator band to make indicator activation.Similarly, also can prepare and soak time indicating equipment when issuing after a visitor.

US FDA has confirmed that aluminium can be directly and Food Contact, and therefore I owe to carry out cooking food with aluminium foil and aluminium dish.

Existing equipment be based on a kind of activator or dyestuff in a kind of matrix, normally indicate in agent matrix and spread.Equipment of the present invention does not have indicator matrix, and described reaction neither be based on diffusion.The change color of present device is due to etching reaction, and therefore a kind of activator can destroy described metal indicator.Described indicator layer is permeable, and reaction only occurs on surface, as heterogeneous reaction.

In existing equipment, the reaction between activator and indicator is heterogeneous, and in equipment of the present invention, this reaction is to react in a kind of matrix heterogeneously, as carried out reacting of liquid activating agent and a kind of solid indicator (aluminium) on surface.Reaction between metal level and acid can produce the hydrogen of a little quality, if especially acid is used as to activator.Hydrogen is not the unique selection of the present invention.But the hydrogen producing is considerably less, because metal level only has-100 dusts thick, therefore it cannot be related to an oxygen containing explosive mixture of generation.The hydrogen of molecular weight minimum can be diffused in the plastic sheeting of equipment.

All indicating equipments that in document, report and this area are used, comprise time and Time-temperature, have a binding that colored materials is fixed in layer, it is adhered to other surface and comprises substrate.Destroyed without any layer in existing equipment.In existing equipment, change the reaction of color and can occur between activator and indicator, they occur in a matrix/binding, make equipment free in maintenance complete.

Aluminium lamination in present device is just bonding with a plastic sheeting without any need for binding.Described metal level is without any binding.Metallic atom is suitable for them firmly bonding.At this moment, destroyed with a kind of bonding agent of activator band or the bonding metal level of pervious course, and be bonded between activator band and indicator strip/substrate, before preventing lamination with special adhesion material, can not lose.

Because aluminium lamination does not have binding/matrix, therefore it is atresia and impermeability layer, and described activator cannot spread.Or even hydrogen (minimum molecular weight) is also difficult to spread on aluminium lamination.Reacting between activator and metal occurs over just layer on surface of metal.

Although creativeness of the present invention has been pointed out in explanation above, and the present invention and existing indicating equipment are (as time and time-temperature indicator, especially label type indicating equipment) between the key distinction, the present invention still has other innovation, and with existing other all indicating equipments, if steam indicating equipment is (as steam, xeothermic, plasma and oxirane), humidity indicating equipment, microwave boils indicating equipment, indicating equipment defrosts/thaws, temperature indicating equipment, food Automatic-heating indicating equipment, electronic circuit, EAS system, pattern, between RFID and similar equipment and method, also also has other difference.

preferred embodiment

A kind of have the metal species material of defined property above and can be used as a kind of indicator in one or more equipment described in the present invention/system.

Term metal, metal analog, metal and there is metallic character in the present invention by the indicator for the equipment of described system alternately.

Indicator can be a kind of common indicator.Common indicator can be a kind of regulator/amplitude modulator.The effect of described indicator can increase or reduce.Sometimes in the time that other meeting reduces effect, two kinds of indicator can act synergistically.Add a kind of common metal, as the indium in aluminium can increase the susceptibility of aluminium to water, if aluminium and/or tin are joined to the reaction capacity that can reduce copper and zinc in copper and zinc.A kind of non-metallic impurities, as carbon and sulphur can be as a kind of common indicator or adjuvants.The crystallinity of metal level and amorphous state also can affect the ability that it and activator react.Add impurity to make metal level more responsive to activator, therefore can be used as a kind of common indicator and use.Described term, alloy, common indicator, regulator and amplitude modulator can be used alternatingly in the present invention.

These materials can be seen a long way off simply, can be made by vacuum evaporation or distillation, it is ambient stable, without bonding agent or matrix, normally opaque, normally antiseepage, monochromatic, can irreversibly be destroyed by a kind of activator, thickness is less than 25 microns, immovable, self is bonding, do not need binding with a base plate bonding, polymerization, only react on surface, and produce an information or image, also can be used as indicator, and preferred indicator.

Most preferred indicator material is a kind of metal or a kind of alloy, and an especially thin layer, for thin foil on substrate or coating, as a metallo-plastic film.Especially preferred metal or alloy is those by nontoxic or safe material as food additives and neutralizing agent, corrosion.LMP metal, copper and alloy are also preferred.Alkali, earth alkali metal, transition metal, late transition metal, group of the lanthanides and radiation metal and alloy thereof can be used as indicator.Aluminium, tin, zinc, copper, manganese, magnesium, nickel, cobalt, iron, sodium, potassium, lithium, calcium, gallium, caesium, germanium, indium and alloy thereof are preferred metals.Aluminium and alloy thereof are the most preferred materials of indicating equipment, are especially coated on a plastic sheeting, as tygon, polypropylene, polyester, nylon, Polyvinylchloride, polystyrene, cellulose acetate and multipolymer thereof.

Can be by various metal alloys as indicator in the present invention.The alloy of aluminium and manganese, lithium, gallium etc. is more responsive to water, and also can be responsive to acid, alkali, oxygenant and salt.Aluminium alloy can accelerate or delay described reaction.According to application, the present invention needs a kind of metal level, and it is more responsive or more than insensitive than aluminum layer.The alloy that more than one metals form, as described in various books, as " aluminum and its alloy ", Joseph R Davis, JR Davis office, the ASM world, metal garden, OH, 1993 and many can be for the preparation of indicator.

Although can use those metals that can produce colored compound, most preferred metal is that those react the metal that can produce colourless or white salt with activator.They comprise as metals such as aluminium, zinc, magnesium product tin.Aluminium is the preferred metal of institute in all metals, and this is due to many reasons, if aluminium and most compounds thereof are all nontoxic.The most compounds of aluminium is white or transparent.Owing to having formed a protective oxide layer, therefore also can relatively very easily react/responsive metal, it is also stable under normal operation.It is a kind of very light metal, and its density is 2.7g/cc, produces the density of (its salt is used as moise-heat sterilization indicating equipment) 11.3g/cc.Therefore, in ink still less, every pound of aluminium can provide higher coverage rate and precipitation.The ink that contains alumina particles can promptly be utilized with the plastic sheeting that scribbles aluminium.

Various aluminum bronze compound uses in industry, and most of for aluminium mass content is 5%-11%, remaining quality is copper or other alloying constituent, as iron, nickel and silicon.Aluminium and other copper, as copper zinc can be used as indicator.

As everyone knows, aluminium has very large negative free energy and forms its oxide.Therefore, aluminium has thermo-mechanical ability to carry out decomposition water.The metal of large negative free energy is preferred indicator.

In vacuum, the water vapour of aluminium is applied on plastic sheeting.One very thin, as standby by this vacuum deposition legal system in the aluminum coating of the various micron thick such as 10 Ethylmercurichlorendimides.The method for optimizing of preparing a kind of indicator layer and a destruction separation layer is a kind of vacuum deposition, vacuum evaporation and splash.

When a kind of metal target, as a canister using as indicator, described activator sprays with becoming band, is coated with, prints or is attached on metal target thing.

Use a metal level to provide another advantage as a kind of indicator, produce on demand safe feature and equipment.The hologram forming on an aluminium lamination is widely used in security conduct amendment indicating equipment.Be used to prepare high security system of the present invention and/or amendment indicating equipment with the aluminium lamination of hologram.A metal level can be used in a nonmetal hologram, makes it to have a high security feature.

Can use more than one different metal layer, as different colours or reactivity, as aluminium (white, and further reaction), copper (redness) and gold (yellow, significant reaction still less) or alloy (as brass and copper).These layers can be separated by a layer of different nature.At this moment a metal level can be served as the effect of a destruction separation layer.

Some indicating equipments, as a Time-temperature indicating equipment, its polymerization based on diacetylene, can be used for temperature-time, Mo Lisi level land, NJ needs a red filtrator protect described equipment not to be subject to ambient light effects.Comparatively speaking, metallo-plastic film is very stable, therefore they can make for protecting a variety of materials in various conventional environment, comprises from surrounding environment, permeating.Therefore the indicating equipment that metallo-plastic film is made has very high environmental stability.

In addition the indicating equipment described in it is important can be noticed simply by user.Reflecting surface is more easily noted than any other surface or color.Therefore, client or storekeeper seldom can not notice this equipment.Similarly, passing of a visitor can be found simply when remote.

Similar, as micro-(as 1-100 micron) side of aluminium, copper, zinc metal and alloy thereof or rounded grain also can be used as a kind of indicator layer after spreading in a kind of binding.Described reaction remains heterogeneous, described induction period by or even longer.This marker makes equipment can keep integrated, or even stop time.

Indicator can be also micro-capsule.Most metals has the oxide skin(coating) of a self-assembling formation, but metallic particles can coated organic thing or inorganics, especially polymeric material.

Layer material produces a kind of very dark color or opacity, and a kind of activator makes it the variation that color or transparency produce an essence, so it also can be used as indicator.They comprise as materials such as the dyestuffs of polymeric dye, polymerization diacetylene and distillation.This indicator can have the separation layer of a destruction, therefore can have longer, a steeper induction period.

A kind of colourless stopping can be printed as an information.This indicator stop that printing district will stay nonreactively, therefore form an information.Being activated agent termination Lv district first will disappear, and then whole layer will disappear very lentamente in ensuing etching.

Metlbond is different from covalency and ion is bonding.Metallic atom can be very strong bonding.Metal electron can freely move towards all directions, and therefore they have good thermal conductivity and electric conductivity.Metlbond can be marine as kation at electronics.Most metals and alloy thereof are solids.Metal can be crystal, can be also phosphorus.

Copper and alloy thereof are also preferred indicator, because copper and brass thing are removed their many bacterium within the time of eight hours, comprise MRS, Escherichia coli and other pathogen.Antibacterial metal is preferred indicator.

Metal (especially filtering metal and alloy thereof), their salt and complex are used the catalyzer for various reactions widely.Metallo-plastic film (comprise metal oxide or the complex of self-assembling formation, synthesize especially from the teeth outwards) can be used as a kind of indicator in those reactions of monitoring.

Semimetal and semiconductor are that element, alloy and compound can conduct between conductor (as 63 x 106S/cm silver) and insulator (lower than 10～6 plastics).A semimetal is a kind of little overlapping material that forms in conduction band and Valence-band.In a metallic conductor, electric current is flowed and is formed by electronics.In semiconductor, electric current is in the electronic structure of material, is flowed or is formed by positron " hole " by electronics.A kind of electric conductivity of semiconductor material is various in external electrical field.Semiconductor equipment comprises transistor, variously penetrates the diode of diode, scr, Digital and analog rectification circuit as light.Solar panels are large semiconductor equipments, and it can be directly electric energy by light energy conversion.The example of semiconductor material is silicon, germanium, gallium arsenide and silit.A kind of semiconductor can be that " intrinsic " or interpolation additive are made P type and N-shaped.If activator is a kind of adulterant, can form so a semiconductor equipment.

Some independent examples of inorganic semiconductor are sulfide (I) oxides of antimony aluminium, boron nitride, gallium phosphide, indium gallium phosphide, InGaP aluminium, cadmium selenide, zinc sulphide, cadmium zinc telluride, lead and copper.

Opaque semimetal and semiconductor can be preferably used for the indicating equipment of native system.

A thin layer of vacuum deposition metal, as sodium, lithium, potassium, magnesium and alloy thereof can be for monitoring humidity or moisture, when these metals and alloy thereof are to moisture and many chemicals when responsive.Can select suitable common metal, regulate the susceptibility of metal level to a kind of activator.For example, aluminium can be by adding many metals altogether, as sodium, lithium and indium regulate to the susceptibility of water.

As many other metals such as copper produce colored compound.By selecting a suitable activator, can produce extra color.The plastic film coating of cupric and alloy thereof and have the ink of copper and alloy particle thereof also can be preferably used for monitoring disinfecting process.

A kind of metal or alloy powder, preferably micron and nanosized, disperses in as a kind of ink or pigment at a kind of binding, and it is a kind of preferred coating composition, in particular for sterilization indicating equipment.The metal reacting with activator rapidly as copper and alloy etc. thereof is preferred metal.Less metallic particles (larger surface area) can more promptly react with activator them, changes.A kind of metal powder in ink or pigment composition and the potpourri of activator are a kind of preferred for monitoring ink or the coating composition of sterilization.Disinfecting process comprises steam, oxygenant, (as hydrogen peroxide and Peracetic acid) and poisonous/harmful gas, as oxirane.

The thickness of metal successive layers (as a kind of metal vacuum precipitation on a plastic sheeting is made) is less than a micron (10000 dust), preferably be less than 0.1 micron (1000 dust), and metal discontinuous/dispersion layer, as formed by metallic particles, its thickness is less than 1,000 microns, preferably being less than 20 microns is preferred size, and more useful to the use of this equipment and preferred method.

Preferably in equipment of the present invention, use the relatively uniform micro-metallic particles of size.Preferably small spherical particles, but can be any other shape, comprise that the granular indicator of irregular side also can use.

The potpourri of two kinds of pigment, a kind of heavier than another kind, they are very important.Owing to applying lighter will mainly floating/float from the teeth outwards, thereby control the color of coating.For example, at the bottom of aluminium ink and copper or copper, alloy ink is to mix at 1: 1, gentlier floats on lip-deep aluminium pigment, the main silver that shows on described surface.When with some selective etch agent etchings, can be first or etching aluminium full out, then produce a kind of brass, a kind of silvery white, then show red.When lighter coloured potpourri, especially organism, they float on the surface upper, therefore their color control.Therefore, can use the potpourri of two or more indicator mixture or a kind of indicator and a kind of non-instruction pigment.

Floating type and non-floating type metallic pigments can be for described indicating equipments.But, in order to make metallic pigments etching better, preferred non-floating type pigment.

Metallic pigments/thin layer as thin as a wafer, as also can using that vacuum coating metal forms.

Inert metal, uses as silver-colored and gold also can be used as indicator, and it and strong activator one are used to monitor and enliven or violent condition, and in normally long-time.

The preferable substrate of metal is a plastic sheeting.But, can be any other substrate, comprise other metal, fiber, paper, wood, adhesive films and glass.For example, a transfering adhesive band, with enhancing paper and the cellulose of thin metal layer, the substrate that can serve as present device uses.

The shape of coating indicator can be arbitrarily, as flat, round, fibrous, cylindrical or other irregular figure.

In the time that a kind of alloy uses as an indicator layer, can be also that one makes etching metal faster, and for some alloys, energy as this in copper (as zinc and copper) obtain change color gradually.

Due to metal indicator layer, one can form indicating equipment, as reaches very high temperature (as 500 DEG C or higher), and activator, substrate and other organic material can bear these high temperature.This equipment also can use at darker low temperature, as 100 DEG C of less thaies.

Copper and many alloys thereof are red or yellow, and mantoquita is normally blue or green.We find when copper and alloy/copper thereof are (as ormolu, show as gold yellow) can react with some activators that can produce green mantoquita, as steam, xeothermic, plasma and oxirane disinfection, can be for red to green variation or gold to green variation.(white or transparent) that aluminum and zinc salt is normally colourless.If the copper producing and alloy salts thereof are actual is transparent, an information, as " stable " is imprinted under coating, it can be worked as when equipment is sterilized and show along with change color.Copper ion indicator also can add for accelerating change color.

Also can replace a kind of metal of dissolve/etching of equipment of the present invention and system by other system.For example, can use silver-colored diamines/wash ammino-complex, this complex compound is in silver nitrate, to add ammonia to be used as a kind of indicator, and glucose is as a kind of activator.This system/method is called as toillen's reagent or test.Glucose can reduce silver complex, thereby forms silver and a kind of metal/opaque surface/coating.The information printing under coating just cannot see.Many other slaines and complex compound and reductive agent, as aldehyde, can use.

Equally, be commonly called as chemical plating process and also can be used for preparing various device of the present invention.In electroless plating process (also referred to as chemistry or autocatalytic plating) technique, can use sensitizer, as stannous chloride, palladium bichloride.A kind of reductive agent, is generally sodium hypophosphite or aldehyde and can reduces the complexing of metal (normally copper or nickel).Therefore, this system also can be used for monitoring the reductive agents such as formaldehyde and their disinfecting process.After metal is precipitated, the information printing under coating will disappear.An information that is printed on palladium catalyst can be electroplated by selectivity.Can an information (as " sterilization ") be become with diverse ways visible, comprise of the present invention these, for example, will be printed on catalyzer or reductive agent information and optionally cover.

Equally, other system also can replace equipment of the present invention and method to carry out a kind of metal of etching or precipitate a kind of metal to form a kind of opaque material.For example, in a kind of alkaline medium, containing the Fehling of copper (II) ion and tartrate ionic complex or Benedict solution can be used as an indicator and uses.Copper (II) ion and tartrate ionic complex can prevent its Kocide SD (II) sediment.Reductive agent, as formaldehyde, can be used as a kind of catalyzer.Aldehyde can reduce copper complex, makes it to become black/opaque cupric oxide (I).And the information being imprinted under coating can disappear again.Therefore, this system also can be used for monitoring the reductive agents such as formaldehyde.

Immersion plating does not need to use extra electric current, just the another kind of metallic coating applying on the metal being immersed in a kind of metal compound solution can be precipitated.The described indicating equipment of another kind of preparation of the present invention is to use a kind of slaine on an activator band, and as hydrogenation copper or copper sulphate, and iron foil, iron particle thin layer are as a kind of indicator.Iron is coated with after copper, becomes redness from white.

In order to monitor radiation, also can prepare a kind of metal of monitoring radiation with so-called photoreduction slaine and complexing agent.The common examples of this reaction is that silver halide arrives silver-colored photoreduction, namely so-called blueprint, and the coating of one of them Ferric Ammonium Citrate and potassium ferrocyanide potpourri is shown in the complex compound that can produce a kind of blueness after light.These photoreductions and photooxidation reaction can be used for preparing radiosensitive equipment, as the radiation dose indicating equipment for monitoring sterilization.

In the above-mentioned non-method and apparatus based on metal etch, described indicator can be a kind of indicator precursor.These non-etching machines also can have various features, as form the information automatically reading.

Except dissolving a kind of metal with a kind of activator, people also can use a kind of activator to dissolve or a kind of opaque or dark material (colourless or white) that expands, and make it to become the transparent various indicating equipment of the present invention of preparing.Described opaque material can be monomer or polymkeric substance.Also can use a kind of impermeability breakable layer of these opaque materials to be used as the indicator of described system.

The finished product of metal ink can be transparent or opaque.According to different needs, can optionally use suitable reactant/activator that opaque material is converted to transparent, vice versa.For example, NaOH and reactive aluminum can generate opaque alundum (Al2O3), add compound, and as sodium phosphate can become alundum (Al2O3) transparently, vice versa.Use the second reaction/reactant, as add another kind of reactant/adjuvant and opaque product to react, the opaque product that dissolves or expand, becomes opaque coating transparent.

For some indicating equipment, as temperature indicating equipment, a kind of activator can be coated on a kind of indicator, vice versa.Described activator and indicator can be the most approaching like this, and therefore reaction is just the rapidest.The activator coating on this indicator first processed, vice versa, then precipitated in a kind of binding.For example, can make in all sorts of ways, as a kind of metallic particles is scribbled a kind of activator by a kind of package method.

Also can use conducting polymer (also referred to as synthetic metal), comprise solubility and insoluble, do not adulterate and adulterate as indicator.Synthetic metal has little and poor spacing.For example polyaniline, the conducting polymer that polyacetylene and polypyrrole mix.Electronic equipment can pass through to use a kind of adulterant as activator, also can be by the neutralization of adulterant is formed for conducting polymer and inorganic semiconductor.

Compound any and described indicator reaction can be used as a kind of activator.Metal also can with activator generation displacement reaction.Metal and alloy/copper thereof can be corroded by a large amount of compounds.The easy corroding metal of water, oxygen, acid, alkali, salt and oxygenant is preferred activator.

A kind of content of activator can be determined by various factors, comprises character and the thickness of indicator, but weight content be preferably～5%, more preferably 10-40%.

Activator can comprise a kind of coactivator.Coactivator can be a kind of regulator/amplitude modulator.It can increase or reduce the effect of described activator.Sometimes two kinds of activation can have synergy.For example, phosphoric acid and replacement or do not replace aliphatics and the potpourri of aromatic sulphonic acid more effective, particularly in water, than more effective in acid separately.A kind of solvent, water, surfactant or plastifier also can be used as coactivator.Some solvent can reduce effect, and other meeting increases effect.Term described in the present invention, coactivator, regulator and amplitude modulator can use interchangeably.

Higher boiling and solid solvent can dissolve a kind of activator, are conducive to the movement of activator, and especially activator and/or pervious course are through a kind of binding.In the time using solvent, can use solid activating agent.High boiling solvent, as styron, xylenol, Phenoxyethanol, diphenyl ether and other a large amount of organic and mineral compounds can be used as the solvent of activator.

We notice that solvent often can accelerate the diffusion of activator and the reaction of indicator, as described in the dissolving of metal level.For example, p-toluenesulfonic acid is the aluminium lamination (25 DEG C of next weeks) that dissolves extremely lentamente 100 dusts as a kind of moisture or water-free activator (100 DEG C dry 30 minutes) in a kind of bonding agent (S8510 AVERY DENNISON), for example, if can make reaction add hundreds of times quickly (, 25 DEG C at 5 minutes) containing the water of 20% left and right.At this with similarly in situation, water is most possible activator, and acid is a kind of catalyzer.

A kind of material, there are one or more performances: with a kind of metal generation metal, change the chemical property of indicator, reduce reflectivity, destroy electric conductivity, variable color, painted, reduce the conspicuousness of described indicator, reduce the opacity of described indicator, reduce the environmental stability of described indicator, do not move past described indicator layer, irreversibly react with described indicator, react in its surface with described indicator, indicator described in basic destruction, this material can be used as a kind of activator.

Reaction velocity will depend on the susceptibility of activator described in metal pair.Weak activator is higher to the requirement of condition, and as higher concentration, temperature and/or longer reaction time, vice versa.

When the agent of needs aqueous corrosion, common mordant, catalyzer or solvent, can use the mineral compound that contains aquation water.Equally, hygroscopic material also can be used as a kind of coactivator.

Because water can be used as a kind of reactant and/or catalyzer, and through being usually used in etching or dissolution of metals, therefore can use moisture organic and mineral compound, water form is therein water of crystallization (usually used as the water of aquation), and it is as activator or activator precursor.Many moisture materials and a substrate chemically combination by this way, therefore it can be removed and can prepare, as heating.For example, anhydrous cupric sulfate is a white solid, and molecular formula is CuSO4.It obtains a kind of crystalline solid CuSO45H2O of blueness after crystallizing out from water.In alum A1K (SO4) 212H2O, there are 12 hydrones.Water is removed in certain temperature or temperature range, and as oxammite and barium chloride can be removed water at about 115 DEG C, and hydrated calcium sulfate can be at about 200 DEG C removal water.

There is higher molecular number water of crystallization, can be Aluminum Chloride Hexahydrate as other salt example of activator, iron chloride and magnesium chloride, eight H 2 O calcium sulphates and baryta hydrate, sal glauberi, borax, sodium borate, sodium carbonate and tetra-na diphosphate, sodium phosphate dodecahydrate diabase, aluminium potassium sulfate, ammonium ferric sulfate, tertiary sodium phosphate, iron ammonium sulfate, aluminium potassium sulfate, sodium ferrous iron and four (4-is to sulfo group phenyl) methane and higher hydrated compounds, as 1, 4, 8, 11-tetra-(2-carboxyl) ethyl-1, 4, 8, 11-tetra-acetazolamide ring tetradecanes (H2TETP) 2, ten hexahydrates and eight water aluminium sulphate.

Activator can be monomer, oligomer, polymkeric substance, single function or multi-functional, for example sulfuric acid, two and H.D aromatic sulphonic acid, polystyrolsulfon acid and polyethyleneimine.

Comprise bronsted-Lao Lai and lewis acid, mineral acid, inorganic and organic acid can be used as activator or catalyzer carrys out etching, especially at a kind of proton solvent, in water.Acid is electrolyte and mordant.The preference of acid is perchloric acid, trichloroacetic acid, hydrochloric acid, sulfuric acid, nitric acid, pentavalent phosphoric acid, phosphoric acid, hypophosphorous acid, methane-sulforic acid, sulfonic acid, benzene, toluene, naphthanol sulfonic acid, camphor-10-sulfonic acid, 3-hydroxy propane base-1-sulfonic acid, carboxylic acid, formic acid, acetic acid, citric acid.Alkyl or fragrant bronsted lowry acids and bases bronsted lowry are all preferred.Partial esterification acid also can be used.Most preferably pentavalent phosphoric acid, phosphoric acid, their derivant and potpourri.Also can use hydracid and halogenohydrin, as ethapon and trichloroacetic acid.

Acid and ester class thereof, comprise that part ester is often used as tackifier.Therefore, acid, as phosphoric acid, can prepare one as non-viscous resins such as PSA, or increases the thickness of PSA.Therefore, can make phosphoric acid form a kind of solid solution, wherein contain matrix/PSA.

Alkali also can corroding metal, and the catalyzer that therefore can be used as activator or activator uses, especially in proton solvent, as water.Some examples of alkali are NaOH, potassium hydroxide, calcium hydroxide, lithium hydroxide, TBuA, fragrant oxide and alkoxide (as caustic alcohol and sodium methoxide, lithium ethoxide and lithium methoxide, potassium ethoxide and potassium methoxide).Amine, as fat, circulation and fragrance, replace or do not replace amine, comprise elementary, secondary and tertiary amine, as ethamine, diethylamine, triethylamine, aziridine, piperidines, pyridine, aniline also can be used as activator use.

Various amine can use.Amine, as single polysubstituted or unsubstituted aliphatics, acyclic and aromatic elementary, secondary, the activator that three grades and quaternary ammonium compound can be used as some equipment uses.The example of amine and salt thereof comprises: amantadine, adenine, aminocyclohexanol, amino lignocaine pentane, amino dodecylic acid, urethanes potassium dihydrogen phosphate, hydrogen sulfate urethanes, penetenoic acid amino acid, aminopropyl imidazoles, aminopropyl pipecoline, amino sorbierite, amino acid undecanoic acid, amino butanol, deoxidation amino-D-glucitol, biphosphate aminoethyl, propyl imidazole, ammonium acetate, ammonia bromine ammonium amino methyl, carbon ammonium, ammonium chloride, ammonium dihydrogen phosphate (ADP), the ferrous hydrate of ammonium sulfate, ammonia formic acid, ammonium bicarbonate, ammonium hydroxide, ammonium iron (meeting) sulfate, ammonium iron (III) FAC (III) three pasture and water acid, ammonium nitrate, ammonium sulfate is every, DAP, Amcide Ammate, ammonium sulfate, benzyl-N-methylethanolamine, benzyl Trimethylamine chloride, two (dimethylamino) benzophenone, chloric ethane amine hydrochlorate, chloro hydroxy oxypropyl trimethyl hydrochloride, the nitrated aniline of chloro, choline, choline chloride, choline, choline iodine, ring hexamine, decyl amine, diallyldimethylammonium chloride, diamines diphenylamine, diamines dodecane, diamines heptane, diamines hydroxy propane, diamines nonane, diamines ether, propane diamine, dibutylamine propylamine, dibutylamine benzaldehyde, diethanolamine, diethylamine, diethyl amido propylamine, diisopropylethylamine, dimethylamine, dimethylaminoethyl alkyl methyl amine ethanol, dimethylaminobenzaldehyde, benzene diformazan the third oxygen amine, diamines propyl group amine, diamino-pyridine, dimethylglycine, two glyoximes, diimidazole, diimidazole alkane ketone, dimethylpropane diamines, diphenylamine, diphenylamine, diphenylbenzidine, lauryl amine, dodecyl Trimethylamine, monoethanolamine, ethanolamine hydrochloric salt, ethylamine, urethane ester hydrochloride, glycidil trimethyl ammonium chloride, histidine, oxammonium hydrochloride, Hydroxylamine sulfate, imidazoles, imidazolidone caproic acid, iminodiacetic acid, methyl amine, methylimidazole, nitroaniline, nitrodiphenylamine, eight decyl amine, phenylenediamine, polyethyleneimine, TBAH, tetrabutylammonium iodide, tetraethyl ammonium, tetraethyl calcium hydroxide, tetrafluoro phenylimidazole, tetrahexyl ammonium bromine, tetramethyl ammonium acetate, tetramethyl ammonium chloride, Tetramethylammonium hydroxide, tetramethylethylenediamine tetramethyl ethylethylenediamine, 4-methyl hexamethylene diamine, methyl-prop, tetramethyl guanidine, triallylamine, triethanolamine, triethylamine, triethylene tetramine, triethylene tetramine hydrochloride, triethyl ethylethylenediamine, tridecylamine, trimethyl ammonium chloride, trimethyl propane diamine, trimethylamine hydrochloride, trioctylamine, three oxygen three decamethylene diamines, triphenylamine, three (methylol) aminomethanes and trimethoxy ethamine.

Although sour, alkali, salt and similar compound are as catalyzer in the etching of metal/indicator, and water is as activator, at this, they are all as activator.

There is a large amount of salt, for example a kind of weak acid and highly basic salt, strong acid weak base salt, strong acid and strong base salt or weak acid and weak base salt can be used as the activator of equipment.Many organic and inorganic eroding chemicals, salt, as aluminum chloride, ammonium phosphorus, ammonium sulfate, lime chloride, iron chloride, lithium carbonate, lithium carbonate, phosphonate ester, phosphate, amine, acid, amine salt, as amine: hydrochloride is (for example, triethanolamine: HCl), Potassium Benzoate, 2,4-dihydroxy-benzoic acid and 2,4,6-trihydroxybenzoic acid potassium, sodium, lithium, sodium acetate, sodium bicarbonate, sodium carbonate, tetrabutylammonium acetate, zinc chloride also can be used as activator.

Preferably phosphorus-containing compound as one of compound of activator.They comprise pentavalent phosphoric acid, phosphoric acid, hypophosphorous acid, organic and inorganic phosphine (PR3),, phosphine oxide (OPR3), hypophosphorous acid (P (OR) R2), phosphorus (P (OR) 3), phosphorous acid (OP (OR) R2), phosphorus (OP (OR) 2R) and phosphate (OP (OR) 3).

It also can carry out catalytic metal with damping fluid and dissolve.In order to maintain stable reaction/rate, can add a kind of suitable damping fluid to make pH value constant.A large amount of damping fluids of reporting in document can use.The example of common buffer compounds comprises: 3-amino propane sulfonic acid { [(methylol) methyl Sanya] }, nitrogen, N-bis-(2-hydroxyethyl) glycocoll, trihydroxymethylaminomethane, N-tri-(methylol) methylglycine 4-2-hydroxyethyl-1-piperazine ethane sulfonic acid, 2-{[tri-(methylol) methyl] amino } ethyl sulfonic acid, 3-(N-morpholine) propane sulfonic acid, piperazine-N's, N '-bis-(2 ethane sulfonic aicd), xylic acid, 2-(N-morpholine) ethyl sulfonic acid, monophosphate potassium, Diammonium phosphate (DAP).

Except using inorganic halide salt, can also use organic halogenation salt as activator or activator precursor.Some representational examples of organic bromine are: alkyl trimethyl ammonium chloride bromide, bromide benzyl tributyl ammonium, to methyl-benzyl ammonium dodecyl bromide, bromide two octadecyl ester ammoniums, dodecyl dimethyl ethyl ammonium bromination DTAB, ethyl triphenyl phosphine bromide, bromide hexadecyldimethyl benzyl ammonium ethyl ammonium, cetyl bromination tetradecylic acid trimethyl ammonium chloride bromide, cohesion amine, poly-(benzophenone tetracarboxylic dianhydride, ethidium bromide), four heptyl ammonium bromines, four (last of the ten Heavenly stems) ammonium bromide, thonzonium bromide methyl bromide.Also can use other halide salts, as fluorine, chlorine and salt compounded of iodine.Halide salt polymkeric substance, as polybrene also can use.These halogenide also can be as the precursor of many chemicals and method.

Gentle and potent, organic and inorganic oxidizer also can with metal and alloy reaction thereof.A kind of oxygenant also can be used as a kind of catalyzer.Conventional representative oxide (oxygenant) comprising: ammonium persulfate, ammonium nitrate, potassium permanganate, potassium dichromate, potash chlorate, potassium bromate, Potassiumiodate, sodium hypochlorite, nitric acid, chlorine, bromine, iodine, cerium (IV) sulfuric acid, iron chloride (III), superoxide is as hydrogen peroxide, manganese dioxide, bismuth sodium, Solozone, sodium nitrate, oxygen, sulfoxide, persulfuric acid, ozone, osmium tetroxide, JV-bromine benzoic sulfimide, tert-butyl hydroperoxide, dimethyl sulfoxide (DMSO), ferric trichloride superoxide, ferric nitrate, formic acid, the urea of hydrogen peroxide adduct, the halogen such as sodium perborate and chlorine and bromine.

There is an oxide layer metal surface, therefore known can be used as metal surface cleaning agent also can be used as a kind of activator or coactivator.Cleaning metal surface is at United States Patent (USP) 7384901; 6982241; 6669786; 5688755; 5669980; 5571336; 5545347; In 5532447, disclosed metal surface cleansing and variation thereof can be used.Some polishing compositions can be used as activator.

Coactivator can comprise sequestrant or complexing agent.Any suitable chemical addition agent of complexing agent, reacts or has weakened the barrier/pervious bed of self-assembling formation or the product of metal reaction and activator.To depend on natural cover or application or intentional pervious bed type in the selection of chelating or complexing agent.The example of chelating or complexing agent comprises, carbonyls (as acyl pyruvic acid), simple carboxylic acid (as acetic acid, aralkyl carboxylic acid), carboxylic acid contains one or more (as hydroxyl acetate, lactate, gluconate, except gallic acid and salt) hydroxyl, enlightening, three, and poly carboxylic acid (as oxalic acid, phthalate, citric acid, succinate, tartrate, malate, edetate (as EDTAP dipotassium ethylene diamine tetraacetate), potpourri), comprise one or more carboxylic acid sulfonic acid and/or phosphine group, etc.Being applicable to chelating or complexing agent can also comprise, for example, enlightening, three, or polyvalent alcohol (as ethylene glycol, catechol, pyrogallol, tannic acid) and amine-contain compound (as ammonia, amino acid whose amino alcohol, two-, three, and polyamines).

Other examples of sequestrant comprise Sodium phosphate (Na3HP2O7), tetra-na diphosphate, sodium hexametaphosphate, sodium trimetaphosphate, sodium tripolyphosphate, PTPP, phosphonic acids, bisphosphonate compound, triphosphoric acid compound, a kind of phosphinic acid compounds salt, ethylenediamine tetraacetic acid, glucose or other chelate compounds.Described sequestrant also comprises phosphonate group sequestrant, as amino three (methylene phosphonic acids), HEDP, HEDP and tetramethyl divinyl enamine phosphonic acids; Aminocarboxylic acidic group sequestrant, as diamines four vinyl acetates and three acetic acid nitriles; Hydroxyl amino formyl sequestrant, as dihydroxy glycocoll; Or their potpourri.

The example of sequestrant also comprises amino acid, as glycocoll, and serine, proline, leucine, alanine, asparagine, asparatate, glutamic acid, valine, lysine etc.; Polyamine compounds and its esters, comprise ethylenediamine tetraacetic acid, N-hydroxyethyl-ethylenediamine triacetic acid, nitrilotriacetic acid, iminodiacetic acid, diethylenetriamine pentabromo-acetic acid and two propylhomoserin ethanol; Polybasic carboxylic acid, comprises phthalic acid, oxalic acid, malic acid, succinic acid, mandelic acid, mellitic acid; The ammonium salt of alkaline metal or acetic acid, citric acid, tartrate, gluconic acid, lactic acid, propionic acid or their potpourris.

A kind of concentration of sequestrant determines by various factors, and as the character of indicator and thickness, preferred weight concentration is more than or equal to～1%, preferred weight concentration is more than or equal to～and 5%.

Also can use and be used as activator, for example chlorination cuprammonium/amine complex and nickel chloride ammonia/amine complex as metal complexs such as transition metal.

Thin layer that pyrophoric material is made or microcapsules particulate can be used as the activator of monitoring oxygen and/or humidity.Described pyrophoric material comprises: metal alkyl, metal alkoxide, non-metallic halide, as dichloro (methyl) silane, Grignard reagent (RMgX), metal hydride or Nonmetal hydride (diborane hydrogen), iron sulfide, partially or completely metal and nonmetallic alkyl derivative (diethyl aluminum hydride, n-BuLi, boron triethyl), metal carbonyl, telluro methane and phosphorus (white or yellow).

The pyrophoric metals of monitoring oxygen and moisture comprises alkaline metal, as metal powders such as iron, magnesium, calcium, as hydrogenation catalysts such as Raney's nickels.

Conventionally water and air can with various metals these metals that react/corrode.But, these reaction for some metals often very slowly.A kind of catalyzer can these reactions of catalysis.The various compound as activator or activator precursor of the present invention also can be used as catalyzer and uses.The various slaines of for example carboxylic acid, as sodium acetate and calcium citrate can use as catalyzer in the moise-heat sterilization indicating equipment as described in embodiment 26 for example.The potpourri of aluminium pigment and sodium acetate is by the steam treatment of 120 DEG C after 30 minutes in a kind of binding, and alumina particles dissolves, and coating becomes light white, be shown as a kind of color of substantially transparent, for example, green, and be imprinted on an information below, as sterilization just becomes visible.But, if aluminium pigment one without any the binding of catalyzer in by the steam treatment of 120 DEG C after 30 minutes, alumina particles is substantially unaffected.These salt solusions such as sodium acetate are under the steam treatment of 120 DEG C, and its pH value can remain unchanged.

The catalyzer using in metal erosion is preferably acid, alkali and salt.Catalyzer is more preferably a kind of as weak acid strong alkali salts and a kind of as the strong acid weak base salt of ammonium fluoride such as tetrabutylammonium acetate salt.Preferred catalyzer is food additives, as sodium acetate and sodium Diacetate.Other preferred catalyst is carboxylate, diacetone, and cyanate, alkali-metal tetrafluoroborate and phosphate, as lithium, sodium, potassium, II family metal, as magnesium, calcium and other metals, as copper, nickel, iron, zinc, and aluminium.Following salt can be with after the steam treatment of 120 DEG C in a kind of binding, dissolved aluminum particle effectively: potassium acetate, lithium formate, calcium acetate, Schweinfurt green (II), magnesium acetate, diacetone lithium, diacetone sodium, diacetone potassium, Zassol, sodium tetrafluoroborate and sodium phosphate.Described coating, in xeothermic (140 DEG C, 30 minutes) lower nondiscolouring, illustrate that water is a kind of activator, and these salt is catalyzer.

Some activators also can start a kind of self-catalysis dissolving of metal.Especially acid, as the hydrochloric acid can be in water at phenixin, poly-chlorinated alkenes and polyvinylidene chloride etc. producing in the radiative process of halogenated compound of the metal such as dissolved aluminum.

Also can corrode a kind of a kind of metal of alloy completely or optionally, a kind of metal of being made by two or more metallic particles potpourri or its alloy, or the upper coating of other metal.These are processed and also can change color.For example, can be in cu-zn-al alloy completely optionally corrosion zinc and aluminium.For example, xeothermic lower processing 30 minutes (dry heat sterilization indicating equipment) by a gold that contains potassium bromate (zinc-copper bronze) printing ink paint at 160 DEG C, just can be under the instruction of color, be that color becomes redness from yellow and comes obviously optionally to corrode aluminium and copper, and corrosion zinc not.If alloy or be arranged on a kind of metal foil coating on other different colours metal can utilize change color to carry out ideally corrosion surface so, therefore reaction can be more effective, more responsive.Equally also can in the granulate mixture of aluminum and zinc/aluminium copper, optionally corrode alumina particles.For example; a kind of potpourri; Yin Mo (alumina particles) and bronze ink (copper and ormolu) that it contains nabam and ratio mixing in 4: 3; it is processed 30 minutes in the steam of 120 DEG C; alumina particles can dissolve; leave red copper particle thereafter, so color becomes redness from silvery white.

For some application, need to use a kind of stronger or larger mordant of concentration as dissolved a RFID antenna or prepare one.Can use strong acid and highly basic, as potassium hydroxide, nitric acid or very active salt, if ferric chloride solution is as a kind of mordant.Also can from precursor, produce these strong mordant, for example sodium nitrite and sodium nitrate are at weak acid, as reacted in phosphoric acid.

Inert metal and many other metals are all difficult to be corroded.Silver and gold are widely used in electronics industry.Money base paint, ink and cream/plastisol are used to manufacture various electronic products, comprise as the printed circuit board (PCB) of RFID antenna.These metals only can be corroded by a limited number of mordant, as nitric acid, and sulfuretted hydrogen sulfides.

Also can, on a metallo-plastic base plate, a photoresist layer be arranged on activator or precursor layer, form electronic equipment, as RFID and printed circuit board (PCB).Described circuit can utilize one to expose photoresistance by traditional method and form.Described activator will spread by more permeate portion, for example, by radiation degradation and corrosion metal below, thereby form described equipment.

This indicating equipment also can use a precursor layer (for example, i.e. a kind of halogenide, halogen compound, sulfide, Nitronium and phosphine compound) that can produce a kind of mordant under irradiating to form on a metal level.On metal, irradiated part can be corroded.Therefore, can form the electronic equipment without photoresistance.

The reaction of some metals can produce hydrogen, and other can (not be commonly referred to substitution reaction).Preferred reaction/activator is not produce hydrogen, but can produce the activator of hydrogen, as phosphoric acid also can use.

Water can be made metallic catalyst.In order to make metallic particles form a kind of colored compound, can use various reactant/activators, comprise salt, sequestrant/complexing agent and dyestuff.For example, if need to form metal sulfide from metal powder, can be with a kind of sulphur source, as element sulphur, metal sulfide, metal thiosulfuric acid, thiocarbamide, thiocyanate and thiocarbamide.Preferred example is potassium thiosulfate, sodium thiosulfate, ATS (Ammonium thiosulphate), barium hyposulfite, potassium metabisulfite, sodium pyrosulfite, 1-(2-methoxyphenyl)-2-thiocarbamide, 1-allyl-2-thiocarbamide, 1-methyl-2-thiocarbamide, 1-ethyl-2-thiocarbamide, 1,3 dimethyl-2-thiocarbamide, 1-phenyl-3-thiosemicarbazides, 1,3-rhenocure CA, 1-benzyl-3-methyl-2-thiocarbamide, 1,3-, bis--oxygen-Toluene-2,4-diisocyanate-thiocarbamide, 1,3-bis--rho-Toluene-2,4-diisocyanate-thiocarbamide, 4,6 dihydroxy-2-sulfydryl and 2-thiohydantoin.Also can use many other compound/indicator as activator, they can form the colored compound with metallic ion, especially be with copper ion, as oxine, styrax or oxime, rubeanic acid (dithiooxamide), cupferron (nitroso-hydroxyphenyl amine), to thiophene ketone, rhodamine and thiocarbamate, also can be used as activator.

Some chemicals can be used for accelerating or the reaction of slowing down.Iron compound and complexing agent, as iron chloride and potassium ferrocyanide and potassium ferrocyanide can accelerate or catalysis as described in reaction.

The general formula of 1,3-diketone is R-CO-CH-CO-R ', and wherein the R ' of R is respectively unit price organic free radical, comprises alkyl, aryl, aralkyl, alkaryl, naphthenic base, alkoxy, alkylhalide group, and there is the alkylhalide group of 1 to 12 carbon atom also can be for the activator of steam indicating equipment.

The potpourri of activator and solution can dissolve or freeze at lower temperature at specific temperature, and they can activate described equipment in predetermined temperature or temperature range.Estimate the humidity that comprises for dissolving indicating equipment and high temperature indicating equipment, micro-wave oven boils, sterilization indicating equipment equipment.These activators are complete deactivations before equipment arrives specified temp.

The present invention can utilize the activator of heat fusing, and its can dissolve at higher than the temperature of predetermined temperature at one mobile.When the activator of heat fusing is in the temperature higher than predetermined temperature, the activator of heat fusing can dissolve, and flows and react with metal indicator in matrix.The activator of heat fusing molten lower than room temperature.This system can be for monitoring 3 grades of sterilization indicator.

Activation precursor material do not react with metal/indicator or react very slow, but no matter be a process or a kind of reagent, the precursor activator of indicator all except.Form, apply, printing, layer and precursor are all activated agent activation similarly.As a kind of activator, a kind of precursor also can be printed on metal/indicator layer or one and be arranged in metal/indicator layer, has a base plate, on the metal level of cover and a precursor layer.

Sometimes between precursor and activator, do not have strict boundary.Various acid of the present invention, alkali and salt can become the precursor in some circulation.Also can be (1) a kind of reactant that can produce activator precursor, it also needs another kind of reactant or the precursor that produces activator, (2) two kinds of reactions can produce a kind of precursor of activator, (3) in the reaction more than a kind of, can produce a precursor for activator, and/or need (4) a kind of catalyzer and analog thereof that can produce activator.Phosphorus, especially white and yellow phosphorus are exactly a preferred example.White phosphorus and oxygen reaction generate the oxide of phosphorus, react and generate phosphoric acid, and phosphoric acid is exactly a kind of catalyzer with water.Therefore, whether white phosphorus is used for monitoring the direct precursor of oxygen as precursor, but reacts with oxygen G&W, produces an activation.Therefore, phosphorus be not directly with the react precursor of generation activator of oxygen G&W.Therefore phosphorus can be used as precursor monitoring oxygen, phosphorus pentoxide monitoring monitoring humidity, phosphoric acid monitoring time and Time-temperature.Precursor or activation and the equipment made thereof can be for multiple uses, as for monitoring multiple flow processs and/or reagent.

Different precursors or activator are difficult to join ink or coating composition, and its reason has one or more, and therefore as crosslinked in them and binding or degraded binding is also just difficult to produce on the spot.The compound of these types can be thought of as the precursor of precursor, but is included in the definition of a kind of activator and precursor thereof.For example, some polyvalent metal ion compounds, as copper, iron, zinc, magnesium, crosslinked, aluminium, nickel, cobalt, indium, the salt of tin and alloy thereof is (as sulfate, phosphate and halogenide) activator that may be, but can not directly add, because they can be cross-linked or precipitate many conventional bindings, as polyacrylic acid.Add a kind of meeting to decompose to generate and add a kind of element (for example a kind of metal, as copper) powder or compound, decompose and produce a kind of activator and another kind of reactant, thereby preparing the precursor of this activator or activator.For example, cuprammonium is a kind of good catalyzer, but it can not directly be added in some ink, because it can be cross-linked many bonding agents.But it can be by adding copper or its alloy particle, for example, be produced out during as precursor at a kind of aluminium that contains sodium ammonium.In a process is processed, such as, sterilization, as steam, sodium bromide can react with copper particle, generates cuprammonium, and it can be used as a kind of catalyzer/activator and accelerates alumina particles dissolving.

Also can be with corrode/dissolution of metals of a kind of precursor, this precursor is in one is processed, as steam with produce activator/mordant xeothermic middle can decomposition.

Precursor can be also organic or inorganic polymer, when it and a kind of reagent, and as radiation, water, humidity, oxygen, toxic chemical, reagent, comprises after chemistry or biopreparate contact, can be decomposed into low-molecular-weight activator.An example is polyphosphoric acids and sodium metasilicate (polymerization state), wherein, when it reacts with water or water vapor, can produce respectively as the activator of phosphoric acid and monomer hydrated sodium silicate.Another example is that halogen polymer is ionized radiation or heating time can generate hydracid.

The reactant that any generation and ETO react is as acid, and the chemicals of alkali and salt may be used to the precursor of ETO activator.Acid, alkali and the salt producing can with a kind of indicator/metal reaction, make metal or metal surface change or dissolve.One metal ion species, if (1) monovalent metal is as sodium and potassium, (2) other monovalence or high-valency metal halogenide, as bromide or iodide, (3) organohalogen compounds, as tetrabutyl ammonium bromide and (four) other salt, comprise organic and inorganic, as sodium thiocyanate etc. all can be used as precursor for the ETO indicating equipment as described in activating.These compounds react with ETO, can generate a kind of as the alkali of NaOH, it can with as aluminium, the metal reaction of copper and alloy thereof.

Any generation and the reactant reacting as hydrogen peroxide and peroxy acid or its isoionic oxygenant, as acid, the chemicals of alkali and salt may be used to the precursor of plasma and strong oxidizer activator.Acid, alkali and the salt producing can with a kind of indicator/metal reaction, make metal or metal surface change or dissolve.Various organic and mineral compounds can be used as activator and monitor hydrogen peroxide and plasma thereof.They comprise alcohol, acid amides, amine, bisulfite, hydrosulfate, carbonate, carbamate, chelate, metal complex, cyanate, ester, halogenide, halocarbon, ketone, nitrite, nitrate, nitrile, nitro, nitroso-, oximes, phenols, phosphate, sulfate, sulfide, sulphite, thiocyanate, urea, polyurethane, salt, Oxidizing and Reducing Agents.Organic and inorganic salts, especially metal halide can be the precursors of very effective activator or activator.These halogenide comprise acetylcholine chloride, bromine ammonium, Choline Chloride, choline iodine, DTAB, glycidyl trimethyl ammonium chloride, potassium bromide, potassium iodide, sodium iodide, tetrabutylammonium iodide, tetraethylammonium bromide, four hexyl ammonium bromides, tetramethyl ammonium chloride tetrabutyl phosphonium bromide phosphorus.

Unsettled some compound also can be used as precursor under certain condition.For example, hartshorn salt is decomposed into ammonia and carbon dioxide.Ammonia can with many metal reactions, therefore can be used as a time, the time, and the precursor of time-temperature indicating equipment use.

Also can use soda acid complex, as amino acid: phosphoric acid, urea: phosphorus pentoxide acid and ferric phosphate complex.

The potpourri of chromotropic dye and halogen compounds can be monitored an ionising radiation as the indicating equipment/quantimeter of high dose (dosage is greater than 10Gy or 1000 rads) widely, as X ray and electronics.Organohalogen compounds, especially as the dyestuff of the polymkeric substance of polyvinylidene chloride polymkeric substance and pH sensitivity can be used for preparing quantimeter, comprise that monitoring ultraviolet ray irradiates.Under ionising radiation, if ultraviolet ray (as 10 electron-volts) is to photon and the electron irradiation of 100 million-electron-volt energy, organohalogen compounds generate halogen acid, and it can change color according to pH value.This halogen compounds and metal can be used for monitoring radiation, the high dose radiation especially using in monitoring sterilization.

Some salt compounded of iodine class, as, diphenyl iodine hexafluoro arsenate and chlorinated diphenyl base iodine can generate matter acid under the irradiation of high-energy radiation, as HCl, and HF, HBF4 and HASF6 (J.Crivello, Chemtech, October 1980, page 624; And " The Chemistry of Halides, Pseudohalides, andAzides ", S.Patai (Ed.), John Wiley, New York, 1983).This sulfonium, iodine and similar compound, wherein main photochemical reaction can generate a kind of super acids, and this super acids can produce other amino acid for catalysis.Therefore, can amplify the variation of color.Such system, United States Patent (USP) 6242154 and list of references disclose.These halogens, sulfonium and similar compound thereof can generate acid and super acids and a kind of metal, they can for monitoring radiation, especially can for monitoring sterilize and perishables radiation in radiation.

In document, do not report use halogen, halogen or sulphur compounds, as the activator (as precursor activator) of monitoring radiation, do not use the indicator of a kind of metal as monitoring radiation yet.The radiation dose of monitoring ionising radiation, if ultraviolet radiation is to the photon of 100 MeV energy, electronics and proton, can develop these systems.Halogen, halogen or sulphur compounds can be used as activator (being precursor activator), and metal can be used as indicator.

A large amount of halogenide can be used as activator precursor and prepares a kind of dosimeter, and it uses a metal level or metallic particles as a kind of indicator.Described halogenide comprises the chloro-1-nitro of 1-, chloroform, phenixin, chloroacetic acid, chloric acid, ethyl trichloroacetic acid, heptachloropropane, benzene hexachloride, methyl trichlorine acetimidate, pentabromo-ethyl chloride, tetrachloroethane, ethapon, trichloromethyl benzyl ester, methyl trichloropropanol hydrate, trichloropropane, trichloroacetamide, trichloroacetic acid, trichloroethanes isocyanic acid, trimethyl benzyl chloride ester, trimethyl propylene chlorohydrin, trichloropropane, commercially available chlorinated paraffin, as the Paroil150A of Dover chemistry, Paroil152, Paroil170, Paroil1061 and Paroil1650, how not, OH and halogenic polymer, as Polyvinylchloride, polyvinylidene chloride, Hydrin and halogen polymer, as polyisoprene and chlorinated polyvinyl chloride.

Other halogenide comprise two [rubigan]-2,2 of 1,1-, 2-trichloroethanes (DDT); Two [p-methoxyphenyl]-2,2 of 1,1-, 2-trichloroethanes, 1,2,5,6,9,10-hexabromo-Cyclododecane, 1,10-, bis-bromononanes; Two [rubigan]-2 of 1,1-, 2-ethylene dichloride: 4,4 '-bis-chloro-2-(trichloromethyl) benzohydrols; Sulfone chlordene bis methane; 2-chloro-6 (trichloromethyl) pyridine; 0,0-diethyl-0-(3,5,6-trichloro-2-pyridyl) thiophosphate; 1,2,3,4,5,6-hexachlorocyclohexanes; N (two [rubigan]-2,2 of 1,1-, 2-trichlorine) acetamide; Three [2,3-dibromopropyl] isocyanuric acid ester; Two [the rubigan]-vinylidene chlorides of 2,2-; Three [trichlorine] s-triazine, and isomeride, analog, homologue, although bromine and iodine compound can be used as precursor, chloride is conventionally stronger than the stability of bromine and iodine compound, therefore chloride is preferred precursor.

Inorganic halides, as bromine and iodine, is photaesthesia compound, uses as ammonium iron (III) citrate also can be used as precursor.

Some can produce the nitro compound of nitric acid under radiation, use as nitro nitric acid and cellulose nitrate also can be used as precursor.

Ultraviolet light absorber can add among precursor layer or on, in the time monitoring high-energy radiation, it can protect absorbing agent not receive the impact of this outside line/sunlight.In the time that metal level is arranged on top layer, best UV protection is indicator, metal level self.。

These halid coatings in a kind of suitable solvent, preferably, in the polymer-bonded thing of one, can be applied on metallized polymer film.

If needed, as the alkali such as amine can be used for neutralizing the acid that those produce for monitoring high dose.

Enter in metal level in order to accelerate acid, preferably make binding be penetrated in produced acid and/or use solvent, as water.Water or its similar solvent/liquid can be used as activator, and acid can this reaction of catalysis.

In order to prevent that acid from entering into atmosphere and/or affecting environmental baseline, a kind of acid is anti-blends protective layer, as tygon, can be arranged on the open surface of described precursor layer.

Can also use the potpourri of a kind of activator and activator precursor.

Have many can be for some equipment, as Time-temperature indicating equipment to indicator and activator.But, most preferred a pair of be aluminium and phosphoric acid.Aluminium is highly stable and nontoxic metal, and phosphoric acid is the nontoxic food additives that use in beverage.Accessory substance, aluminum phosphate is water insoluble, also non-toxic, can be used as deodorant and uses.

Acid, alkali and salt can be used as activator, and therefore their reaction can be by pH value, and the dyestuff of kation and negative ion sensitivity is monitored.For example, bromophenol blue and alkali, as NaOH contact can become blueness.When blue bromophenol blue and acid, as acetic acid contact, can there is a series of change color, as blueness becomes green, then become yellow green then yellowing.Aluminium ion reacts with alizarin and obtains a red sediment; Copper ion reacts pulverize purple with cuproine, ferrous ion and 2,2 '-dipyridine produces red, and ferric ion and ferrocyanide nak response become blueness, magnesium ion and examination magnesia mixture, and nickel ion, dimethylglyoxime reaction becomes redness.Detect mineral compound, the method for their kation and negative ion is also known, and the method is relevant with change color.These reactions and corresponding compound also can use at described equipment, if while especially also needing change color.The indicator of mineral compound and detection thereof is open in following document: J.Bassett, R.C.Denney, G H.Jeffery and J.Mendham, Vogel ' sTextbook of Quantitative Inorganic Analysis, Longman Scientific and Technical, p.294,1986.; FritzFeigl, Vinzenz Anger and Ralph E.Oesper, Spot Test inInorganic Analysis, Elsevier Publishing Company, 1972, p.526-616.; Products forAnalysis, Catalog ofHach Company, 1986-87 (quoting as a reference in the present invention).

These dyestuffs or compound always react at first generation change color with activator, therefore can be used as indicator and indicate the activation of described equipment.These are conventional pH value dyestuffs.These dyestuffs are coated on aluminium lamination or pervious course.Preferred material is a kind of coloured dyestuff, and it can become colourless after contacting with activator.A thin layer of activation indicator can be coated on metal level with various painting methods, comprises sublimation dye method.Reaction between activation indicator and activator is always being used as label in a flash, and it can use hundreds of labels in one minute, therefore can monitor activation, and the variation of color should be fast as far as possible.Reacting always flashy between phosphoric acid and pH dyestuff.This is very preferred performance.Only on indicator strip, use a kind of activator and do not mean that described equipment is activated.Described activation indicator, by confirming that described equipment is activated, is also visually visual.

Current equipment has some internal indicators to monitor to distort.The uniformity coefficient of aluminium lamination, damage degree, it is destroyed, forms end-product, as the method for aluminum phosphate etc. can be monitored amendment as middle indicator.Also can add some middle indicator.Amendment indicator also can physics use, avoid some harmful effects, as humidity, oxygen, the impact of light etc.

A large amount of reactions all can produce change in fluorescence, instead of macroscopic change color.These compounds can be used as indicator, and they are safe to equipment.The all colours here can be also fluorescence color.

We have tested a large amount of organic and mineral compounds.In a metal (aluminium of 125 dusts) mylar, add a kind of mineral compound and several dripping, mediated a plastic foil on bonnet, prevented the evaporation of moisture.In one day, observe under room temperature He at 60 DEG C and dissolve the required time of this metal level.

Following compound can dissolve aluminium lamination (under room temperature required several hours) very fast: ammonium ferric sulfate [III], acetyl barium, baryta hydrate, bismuth nitrate [III], calcium acetylacetonate, lime chloride, calcium hydroxide, calcium sulfide, cobalt ammonium, cobalt chloride, cupric chloride, iron salicylide, iron sulfate [II], diacetone lithium, lithium hydroxide, lithium tantalate, mercuric acetate, mercuric iodixde, nickel chloride, palladium bichloride [III], palladium nitrate [III], phosphoric acid, phosphorus pentoxide, acetyl potassium, sal tartari, potassium hydroxide, potassium iodide, potassium phosphorus, potassium ammonium, silver sulfate, sodium carbonate, diethyl sodium, fluorine sodium carbonate, sodium fluosilicate, NaOH and tetrafluoro sodium carbonate.

Following compounds can be dissolved aluminium lamination (60 DEG C of next days) lentamente: aluminium acetylacetonate, aluminum chloride, nitrous acid aluminium, aluminum phosphate, aluminium sulphate, ammonium dihydrogen phosphate (ADP), ammonium sulfate ferrous ammonium, iron sulfate [II], ammonium oxalate iron [III], iron ammonium oxalate [III], phosphorus ammonium, cadmium sulfide, calcium bromide, lime chloride, calcium oxalate, calcium pyrophosphate, cerous carbonate, acetylacetone cobalt, cobalt hydroxide, cobalt oxalate, cobalt sulfide, copper, diacetone Schweinfurt green, cupric thiocyanate, copper benzoate, dimethyl amine boron, diacetone acid amides iron, iron gluconate [III], iron sulfate [III], iron chloride [III], ferric bromide [II], ferric bromide [III], lithium chloride, lithium formate, lithium nitrate, magnesium acetylacetonate [II], magnesium acetate, magnesium sulfate, magnesium oxide, nickel bromide, the potassium ferricyanide, potassium ferrocyanide, silver acetate, silver nitrate, acetyl sodium, niter cake, sodium bisulfite, niter cake, niter cake, Zassol, sodium hydrosulfite, caustic alcohol, sodium hexametaphosphate, sodium bicarbonate, dibastic sodium phosphate, hydrated sodium sulfide, sodium nitrite, sodium oxalate, sodium phosphate, sodium sulphide, sodium sulphite, sodium thiocyanate, sodium thiosulfate, diisopropyl ester zinc acetate, zinc paste and zinc sulfuric acid.

Following compound has only dissolved a bit or has not dissolved at all aluminium lamination under described condition: aluminium hydroxide, aluminium sulphate, ATS (Ammonium thiosulphate), ammonium acetate, ammonium bromide, hartshorn salt, ammonium chloride, ammonium sulfate, barium acetate, barium bromine, phenyl boric acid, borine ton butylamine, boric acid tin butyl ether, cobalt phosphate, dibutyl tin maleic acid, gadolinium oxide, magnesium sulfate, silver sulfate Zassol.These compounds, under stronger condition, as higher humidity, can dissolve aluminium lamination or dissolve other more reacting metal and alloy under higher concentration.

In another experiment, the above-claimed cpd/activator of 0.5g left and right is dissolved in the Joncryl77 (S.C.Johnson and Sons, Racing, a kind of polypropylene binding of WI) of 4g.Some of them can not be dissolved, and other can make Joncryl 77 precipitate.Add excessive ammonium hydroxide can again dissolve Joncryl 77.This potpourri is coated on metal (aluminium of the approximately 125 dusts) mylar of 100 microns, and with the wire intertwist of #20 and #40, to bar, 70 DEG C dry.Workpiece is exposed to 100% humidity, lower 1 day of the temperature of 60 DEG C, lower 30 minutes of 120 DEG C of steam, lower 6 hours of the humidity of oxirane 100% saturation degree and the temperature of 50 DEG C, lower 6 hours of the hydrogen peroxide vapor of 50 DEG C, 160 DEG C xeothermic lower 30 minutes.Their major parts have all been dissolved metal level, only have one, can dissolve described metal level more than a kind of activator and some activators after all processing.For example, (1) ammonium thiocyanate, potassium ferrocyanide, dissolution of metals layer in sodium iodide and zinc chloride meeting hydrogen peroxide, (2) diacetone lithium, lithium chloride, lithium formate, potassium acetate, Potassium Benzoate, potassium bromide, potassium chloride, potassium formic acid, potassium ferrocyanide, sodium acetate, sodium bromide, diethyl disodium, sodium thiosulfate, sodium thiocyanate, sodium sulphite can be in oxirane dissolution of metals layer, (3) lime chloride, potassium acetate and sodium carbonate can be at the xeothermic middle dissolution of metals of 160 DEG C, (4) lime chloride, acetyl lithium, lithium formate, potassium acetate, potassium ferrocyanide, potassium formate, sodium acetate, sodium sulphite and sodium tetraborate can be in the steam of 120 DEG C dissolution of metals layer.Therefore, by selecting suitable activator and concentration thereof, cementing agent and other adjuvants, can make self to read steam indicator can be optionally only for one or more processing/chemicals.

In another experiment, to aluminium ink (the Braden Sutphin that adds about 3g in the above-mentioned mineral compound of about 0.5 gram, the product of Milwaukee WI, it is numbered 9W2967J) and bronze ink (zinc-copper bronze of about 3g, the product of Braden Sutphin, it numbers 9W3021N), mix heating while needs.

Some compound reacts within a few minutes, and some and bonding agent are crosslinked, and that remaining is still is mobile.Described flowing mixture scribbles #20 wire intertwist bar on the mylar of 100 microns.At 60 DEG C of film coatings dry approximately 15 minutes.Diaphragm is cut, and the xeothermic middle processing of 140 DEG C 30 minutes, the xeothermic middle processing of 160 DEG C 30 minutes, at 100% humidity and 60 DEG C 16 hours, in the steam of 100 DEG C 30 minutes, in the steam of 120 DEG C 30 minutes, pass into the humidity of oxirane and approximately 50%, in the temperature of 40 DEG C and hydrogen peroxide steam, process 6 hours.Above-mentioned activator major part has all been dissolved alumina particles and bronze particles.

A kind of ink that metallic particles is made can be coated on word, as " sterilization " (as preferably green) or be printed on green/symbol at one.When the metallic particles in ink has dissolved in disinfecting at one, information so, as " sterilization " can manifest.

Conduct of the present invention is auxiliary, accelerates, and effectively mobile solvent or the liquid of catalyst activator comprises following various: water, 15 aliphatics of chloro-carbon, aromatic series and aliphatics and aromatic series substituted amide, preferably acetamide, dimethyl formamide and chloroacetamide, alcohol, preferably amylalcohol, n-hexyl alcohol, dichlorohydrin, ester, preferable methyl propionic ester, valerate, diethyl maleate, ethylene glycol bis sodium acetate, ethyl salicylate and triacetyl glycerine; Nitroparaffin, preferably nitropropane; Aldehyde, preferably butyraldehyde, carbonate, preferably ethyl salicylate and propylene carbonate; Aromatic alcohol/phenol, preferably benzene hydroxyl, phenmethylol, phenol; Amine, preferably diethanolamine, dimethyl cyclohexane diamines; Ether-ether class, preferably ethoxy ethyl acetate, trioxymethylene, dimethyl ether tetraethylene glycol, phenetol, phenyl, propylene-glycol ethyl ether acetate and propylene glycol butyl ether; Alcohol ester, preferably glycolic acid ester; Amino acid, preferably glutaric acid, isobutyric acid, mandelic acid, p-toluenesulfonic acid; Ketone, preferable methyl ethyl ketone and hydroxy benzenes; Ketone ester, preferably methyl acetoacetate; Lactone, preferably propiolactone and butyrolactone, methyl pyrrolidone and their potpourri.People can use more than one activator solvent in varing proportions.Also can use adjuvant, as cosolvent (organic solvent of especially high polarity, as alcohol, acid and amine, ether) surfactant and nucleator.A kind of wetting agent that these solvents also can be used as in activator band comes moistening metal surface.

The preference of solvent comprises butoxy-2-ethyl stearte, butyrolactone, DEF, dimethyl maleic acid, dimethyl carbonate, dioctyl phthalate, glycol dimethyl ether, ethyl salicylate, Polyethylene glycol dimethyl ether, carbonic allyl ester, vinegar ester, phenylate, dodecyl-1, 2-methyl pyrrolidone, ethoxy ethyl acetate, ethylene glycol bis sodium acetate, ethyl trichloroacetic acid, methyl pyrrolidone, the methyl sulfone of different molecular weight, , dimethyl formamide, cyclohexane, phosphorus, dioxane, tetrahydrofuran, P-xylene, acetone, butanone, ethyl acetate, propyl acetate, toluene polyglycol, dimethylbenzene, normal hexane.These solvents also can be used as a kind of wetting agent in activator band.

Solvent also can be for the preparation of pigment of the present invention, ink and plastics.

Because the reaction of activator (acid is liquid normally) and indicator (aluminium) is various, therefore can use a kind of phase transfer catalyst, and wetting agent, as surfactant, also can be used for accelerated reaction, improve the consistance of reaction.Can carry out with wetting agent the metal of humid zone phosphoric acid.High boiling wetting agent can be stablized bronsted lowry acids and bases bronsted lowry, especially can in the electroplate liquid of soda acid, use.

Activator can contain a kind of solvent and/or surfactant carrys out the humidity of even indicator and reacts uniformity coefficient.A large amount of surfactants is commercial, comprising: alkylphenol-polyethenoxy, polyoxyethylene ester, polyoxypropylene ester, long-chain fat salt and sulfonate, polyethylene oxide and polypropylene oxide.

For some application, as the activator band of Time-temperature indicating equipment can, by mixing a kind of activator or a kind of precursor and a kind of binding/a kind of bonding agent, as prepared by a kind of PSA, and be applied on a base plate, as a plastic sheeting.Application of coatings technology can be for being coated in activator/matrix on a base plate the most widely.A charge releasing belt can, for rotating activator band, make it to be stored.

Some as the equipment of Time-temperature can be by using activator band or vice versa is activated on indicator strip.Described equipment is activated rear low-temperature storage, until it is used on an object.Equipment of the present invention can be sealed in its periphery, prevents that activator from moving or and environment reaction.Can heat to realize sealing, or realize with a kind of non-permeation coating.

When indicator is during to gas and vapor sensitive, described equipment can be activated while contact with steam with these gases.For example, after a kind of metallic coating to oxygen and water vapour sensitivity contacts with humidity/steam with oxygen, can be activated or can be for monitoring them.

According to a side of applying and equipment is looked, expired marker can be higher or lower than this indicator base plate.If indicator base plate has color, base plate self can be an expired marker so.This message can be imprinted on base plate or under, but preferably below marker.Coloured plastics film is existing, does not therefore need to apply, if only need a kind of color to be used as a kind of expired instruction.

If chemical reaction detects the infiltration of coating material, on instruction material, can apply top or protective seam.For example, the protective finish of permeable steam or film can be applicable on steam indicating equipment and permeate oxirane for oxirane indicating equipment.Protective finish can reduce around or the harmful effect of environmental baseline as much as possible.

Although the present invention does not specify color reference chart, it can use.Particularly useful in the time of needs forced use color reference chart, become tradition/routine or preferential.The present invention's color reference chart used be similar to described in prior art file device or market on used.Color reference chart can be any shape as circle, rectangle, square with similar and have one or more for judging the color reference bar code of different phase of storage time limit and process development.Color reference bar code can or have as seen or become when needed visible additional layer by one on any layer.

The indicator strip with a thin metal layer (as, approximately 50 dusts) is by short and a mild induction period are provided, so mild change color can be provided.The indicator strip therefore with a thin metal layer can be used to manufacture and is similar to the indicating equipment as seen or do not have on those markets with color reference chart.

There is a metal strip layer (for example, approximately 50 dusts), will provide progressively induction period shorter, therefore progressive coloured variation can be provided.Therefore, there is the indicator layer of strip index can be used to manufacture similar indicating equipment use or not use color reference chart to sell on market.

Indicating equipment can be both from reading, and can be also to have or do not have color reference chart.

Although for stop instruction information and color can be arbitrarily, preferably selecting is grey because in the time of aluminium lamination attenuation aluminium lamination grizzle.

Information Level can, below aluminium lamination, be printed in advance on its substrate before metallization.

The size of indicating equipment may diminish to several square millimeters to several centimetres even larger (as, can be several square metres if needed).The thickness of equipment were typically thousand/centimetre to millimeter or if need can be thicker.

Equipment can be also the band shape of growing very much, can be used in any object and comprise on the chest that contains food product packets, or cut into little slip Ying Yu on independent object.The long place that closes that also can be used on perishable thing container with shape indicating equipment, therefore can notice and monitoring to storage period easily.

This equipment can also be large label, paster and similarly form.

Because the marker of current device is highly stable to environment, it is activation that indicator strip can be applied in that then the container that comprises perishable thing on any object need in advance, as in the time that container has been filled perishable thing.

Indicator, the thickness of activator and other layers as required can be different.The thickness of indicator layer can be different thin as 10 dusts to 0.01 millimeter.But the thickness of other layers is within the scope of about 0.001 millimeter to 1 millimeter, preferably at 0.05 millimeter within the scope of 0.5 millimeter.General, the different-thickness of pervious course is with for the needed asynchronism(-nization) of change color.

Activator concentration in activator matrix can be 0.01 to 0.9g/cc scope of matrix and most preferably matrix 0.05 to 0.5g/cc.The concentration of the adjuvant (except any chemicals of activator and indicator) in any layer can be 0.01 to 0.2g/cc.The concentration of indicator will be very high, approach 100% (as being only aluminium) and if coloring agent be used to indicate agent can be higher than 30%.The preferably thinner layer of indicator.Same, if opaque layer is used in equipment, the preferably thin as much as possible and higher opaque layer of colorant concentration.

Replace after metal level and at other place color coatings, can have coloring agent or pigment by apparatus, or comprise that with bonding agent coloring agent or color-printed have the PSA active agent layer of information.

With steam and sanitizer and/or with additive method with said comprise the time here, the raw material of Time-temperature makes to be used for write information and fades and variation from coloured to colourless as the ink of " not the having " of " not sterilization ".For example, many coloring agents can fade with hydrogen peroxide and steam.The performance that some raw materials contain coloring agent, as become colourless when being exposed to sodium thiocyanate in oxirane.In the time processing, as sterilization, " not having " information becomes invisible.

In the time that ink is made up of metallic particles and is used as indicator, activator must be diffused into indicator from bonding agent.This equipment may have some diffusion property and diversified response characteristics based on equipment.

Pervious course, wedge shape or flat shape can have neutralizing agent.Also may there is extra neutralizing agent layer.Pervious course may be polymkeric substance neutralizing agent, as polyacrylic acid or polyethyleneimine.

Preferably, make the method for belt and some equipment, as the making of time and time-temperature indicator, indicator and indicator strip store with the form of parent roll until need to make indicating equipment time.Reel can be loaded on suitable processing equipment/equipment subsequently.For activation equipment, take away after releasing layer and be applied on the dependence object on indicating equipment and application.Commercially available tag application equipment can use.This equipment can preactivated (being that activator is applied on indicator strip) and being freezing at a lower temperature, as deep-freezing or dry ice.This activation indicating equipment should keep low temperature until be applied on object.

Some solid substrates can be as the substrate of indicating equipment.Preferred substrate is a kind of flexible plastic sheeting and nature (fiber) and synthon (polyolefin as bonding in staple fibre belongs to synthetic paper as spy defends strong R) paper.Fiber reinforcement substrate can be used for band indicating equipment.Plastic substrate can own colored (pigment) or painting last layer color.It can be transparent, translucent, bright or various strong colored.Mylar comprises polyolefin (linear pattern or a line style), polyamide, polystyrene, nylon, dacron, polyurethane, polysulfones, phenylethylene-maleic anhydride, styrene-acrylonitrile, the ionomer of the ethylene methacrylic acid salt based on sodium or zinc, polymethylmethacrylate, knit dimension element, acrylate copolymer (acrylate, as ethylene methacrylic acid, ethylene methyl acrylate, ethylene acrylic and ethylene ethyl acrylate), polycarbonate, viscose paper, polyacrylonitrile, ethene ethene acetate and their multipolymer can be used as the substrate of equipment.Preferred substrate is tygon, polypropylene, dacron, cellulose acetate, polyvinyl chloride polymer and their multipolymer.Substrate can also be infiltrative, as the nature of some application or synthetic paper and fiber.These substrates can metallize.

Substrate can be that any thickness is to be applicable to intended purpose.The thickness of substrate can be in the scope of about 8 to 500 microns.Preferred thickness is 25 to 100 microns.

Bonding agent or viscoelastic material, as comprise synthetic rubber, acrylate, organosilicon, the use of synthetic latex and vinyl acetate, is a kind of preferred material for psa layer as the pressure-sensitive adhesive (PSA) of exemplary.Included pressure-sensitive adhesive has as the elasticity of elastic component or rubber polymer and low-molecular-weight tackifying resin viscosity composition.Conventionally the rubber based on pressure-sensitive adhesive comprises natural rubber, synthetic rubber, and as neoprene, polyurethane, and the multipolymer of the random block of styrene-butadiene, isoprene-styrene block copolymer, polyisobutylene, butyl rubber, and amorphous poly propylene.Explain, but be never to repel, comprise natural rubber applicable to the viscoelastic material inventory of indicator of the present invention, butyl rubber, polybutadiene and they and vinyl cyanide and cinnamic multipolymer, Poly alpha Olefins (PAO), as polyhexene, poly-octene, and the multipolymer of they and other, polyacrylate, neoprene, silicone pressure-sensitive adhesive, and segmented copolymer, as styrene-isoprene block copolymer, and above-mentioned any potpourri.Contact adhesive can comprise, as, polyisoprene, amorphous poly propylene, and polybutadiene, polyisobutylene, organosilicon, ethylene vinyl acetate, or acrylate based on pressure-sensitive adhesive, and the typical case tackifier and/or the plasticiser that comprise.Bonding agent also comprises Isooctyl acrylate monomer (IO A) or the Isooctyl acrylate monomer/acrylic acid (IOA/AA) based on pressure-sensitive adhesive.

General acrylic acid adhesive, as acrylic acid-2-ethyl caproite, butyl acrylate, ethyl acrylate and acrylic acid can use.These acrylic acid adhesives be nature to presser sensor.The polymkeric substance of vinyl ether and multipolymer, as methoxy ethylene, ethyl vinyl ether and isopropyl-ethylene base ether are as pressure-sensitive adhesive.The organosilicon natural gum of two types, 1) all methyl alkali and 2) phenyl of improvement can be used as pressure-sensitive adhesive equally.Organic siliconresin, as tackifier and by adjusting resin and gummy ratio, can be manufactured the adhesion characteristic of wide region.Tackifier containing high organosilicon natural gum is clamminess very much.Organic silicon adhesive passes through catalyzer equally, as benzoyl peroxide and amino silane, next crosslinked (solidifying).

Hot melt pressure sensitive adhesive generally includes by segmented copolymer, and tackifying resin and plasticizing oil composition use.Segmented copolymer provides the toughness of adhesive surface, the characteristics such as integrality and slickness.Further also provide tackifying resin and oily dissolving and the suspending medium of plasticizing.Tackifying resin is tackified and clinging power and reduction viscosity, and plasticizing oil reduces face value, viscosity, glass excess temperature and energy storage modulus and increase toughness.

Equally, can solidify glue with ultraviolet light and hydrogen peroxide.In precursor, add activator and solidify with hydrogen peroxide or with radiation.

Preferably, the PSA of simple supply need to or not affect activator with the fastest speed and minimum influence activator.Some acrylate can for but great majority are not suitable for some activator, as strong bronsted lowry acids and bases bronsted lowry.

Preferably PSA but other bonding agents also can use.

For some equipment, as persond eixis equipment or visitor's identification card, its first-selected psa layer and marker bonding more firm, is therefore not easy to be repaiied.

Many water-soluble/swelling type polymer system, as those are based on plasticising and polymethylmethacrylate non-plasticizing, polyglycol, cellulose ether, polyvinylpyrrolidone, poly-MEE, poly-aminomethyl acrylate, polyacrylate, the multipolymer of methyl and/or ethyl ester acrylic acid and methacrylic acid, vinylpyrrolidone/vinyl acetate, vinylpyrrolidone, methacrylic acid, methyl methacrylate and natural prodcuts, as dextrin, gelatin, casein and starch, can be used for the bonding agent/PSA of the activator of monitoring humidity/steam.This system is disclosed in U.S. Patent number 4215025,4331576,4490322,4775374,5133970,5296512,5296512,5395907,5565268,6326524,6444761 and 7465493, U.S. Patent application 20090018514,20090030361 and 20090062713 and WO/1995/005416, WO0230402, WO0021582 and WO0154674 and reference, the molecule that here exemplified and method can be used as the bonding agent of activator and indicator equally.Range of application of the present invention is now included in these patents and patented claim in.

Releasing layer can by that and PSA that I guess very faint bonding the or gluing material of not being stained with also not having form.Releasable material comprises organosilicon, and fluoropolymer is as teflon, highly cross-linked resin and oil.Preferably releasable material is organosilicon and fluoropolymer.

The material of gel form can be used as bonding agent equally.Crosslinked or crosslinkable polymkeric substance equally also can be used.They comprise natural and synthetic polymkeric substance, as gelatin, and agar, " super slurper ", this is a kind of 60% sodium salt and starch, polyacrylamide and acrylic acid graft copolymer.Using the advantage of super slurper (product of the aldrich chemical company of commercially available Milwaukee, the state of Wisconsin) is at room temperature to form gel, does not need to use the heat cool to room temperature by following.And can use multiple polymers, multipolymer and their potpourri obtain desired characteristic as bonding agent, as high gel strength and high gelation temperature.Preferred polymkeric substance can keep solvent and activator.Can be used for equally these equipment by the water insoluble polymer that gelling forms in solvent and non-solvent association.Book is below same available with the polymkeric substance that the reversible gelling of listing in document forms: (1) " reversible gel polymkeric substance and related system ", Borrow S drag-line, the symposial series #350 of ACS, Washington D.C., 1987, ACS symposium #350 collects, Washington D.C., 1987; (2) L.L. enjoys strange and J.K. West, chemistry summary, 90,33 (1990); (3) " hydrogel ", Nagasaki and K. sheet ridge, Kai Tai, P23 in March, 1997; On June 9th, 1997, " E & E NEWS " periodical, P26, " encyclopedia of polymer science technology ", 7,783 (1986); (4) " reversible crosslink " polymer science technology, 4,395, (1986), L.Z. Roger Ge Weina and GL. Suo Luoni Meath gram, and Russia's chemistry summary, 43,503 (1974) and (5) " macromolecule handbook ", A. Xi Er Tener, this moral Edison (J. white orchid dupp and E.H. Yi Meiguteaidisi), John Wei Li and Sang Si, New York, 1989.

Here the anti-activator mentioned is as " facial mask ", and " resisting " " obstacle " or " anti-etching dose ", in typical case's application of indicator layer, are in most cases the positions that only covers desired indicator layer.The anti-activator here and anti-etching dose can be replaced.Anti-activator and indicator layer are bonding and at least within certain scheduled period, and the impact that the cover part that prevents indicator is subject to it becomes impermeable.Conventionally, the pervious course of indicator at least can be prevented from or reduce its diffusion.

The type of activator and equipment is depended in the selection of anti-activator.Preferred anti-activator raw material is polymkeric substance.Here list most polymers, comprise metal and some organic and mineral compounds, it can be used as resistance agent or Inhibitors is resisted activator, as long as they stop the infiltration of activator.As the polarity of activator, nonpolar or low polar polymer, as tygon, polypropylene, polybutylene and polystyrene, will be good resistance agent.

Obstruct/protective seam/coating can be organic, inorganic or organic metal.It can be basic crystalline solid or noncrystal.Coating may be pottery, if inorganic oxide is as aluminium oxide, and tin oxide, salt is as halogenide and phosphate.In the time that metal is used as barrier layer, it also can be used as indicator and barrier layer.The metal oxide layer of a lot of self-assembling formations.This passive layer is different from other oxides as phosphate and chromate.It can be also other metal levels or lip-deep application layer.Barrier layer can be continuous or granular and porous.Barrier material may be also resistant material.

Obstruct/protective finish can pass through as sputter, physical vapour deposition (PVD), and chemical vapor deposition, thermal evaporation, electron beam evaporation, pulse laser ablation, cathodic arc evaporation, ion beam depositing, anodization, transforms, powder, collosol and gel, electroless plating and electro-plating method deposit.

The thickness of barrier layer depends on the type of barrier layer.It can be from several dusts to millimeter.

Obstruct/protective seam should be able to decompose by physics and/or with the chemical reaction of activator or activator precursor.Can collapse broken or to separate broken layer be that a kind of migration for activator can be by the material of physics or its type of chemical modification, it comprises and collapses brokenly, degrades, and fragmentation, dissolves, fusing, peels off, cracked, and fracture, breaks, division, splits, decline, the transformation under glass transformation temperature and phase transformation.

Obstruct/protective seam equally can with activator, activator precursor and/or additive reaction or form compound.Chelate can be added on active agent layer and divide barrier layer.Can be used on active agent layer for the solvent that dissolves barrier layer.Most preferably activator reacts and destroys barrier layer, as becomes pervious course.

These equipment can have and intercept and permeate two-layer (or barrier layer but become under certain conditions pervious course) in active agent layer.In some cases, if metal is as aluminium, barrier layer can naturally form as materialization effect.Indicator layer can have one deck natural shape stratification and other layers that are applied in natural shape stratification.These layers can be a kind of organism and another kind of inorganics.

While can be observed use metallized polyester film induction period, on the aluminium lamination of indicator, can form oxide layer.When drip 85% phosphoric acid on metallized polyester film time, there is no obvious reaction in nearly five minutes, then after six minutes, on metal level, form bubble (because producing hydrogen) and this layer and become clean.Within five minutes, do not produce hydrogen and can show that phosphoric acid may be to react with the aluminium oxide layers at top.The generation of hydrogen is to show that phosphoric acid and metal start to react after aluminium oxide layers destroys.Weak acid dissolves as phosphoric acid spends the longer time possibly.This shows that energy of activation low (lower than 10 kcal/mol) may be owing to destroying alumina layer.When in the time that metallized polyester film drips ferric chloride aqueous solutions, metal starts only to move to center gradually in the dissolving of the edge of solution boundary line.This may be due to the protective effect of its oxide to aluminium lamination.

Conventionally between resistance and barrier material/layer, only has very little linear boundary line.

Here defined pervious course is the layer of a permeable activator.Any material can allow activator diffusion or migration just can be used to make pervious course under controlled conditions.Excellent pervious course is polymkeric substance.The type of pervious course depends on activator.It is mainly used to change/increase transparency the energy of activation that changes the needed time and change reaction/equipment.Pervious course material comprises glassy polymers, semi-crystalline polymer, physics and chemistry cross-linked rubber, intersegmental polyester, polyamide, radiation crosslinking polybutadiene, and pressure-sensitive adhesive.Applicable glassy polymers comprises polystyrene, polyvinyls and halogenated polymer, and as Polyvinylchloride, Hydrin, and acrylate is as polymethylmethacrylate.Applicable semi-crystalline polymer comprises tygon, polypropylene and polyester.Applicable physical crosslinking rubber comprises segmented copolymer, as SIS, and intersegmental urethane rubber.Applicable chemical crosslinking rubber is sulfur-bearing natural rubber crosslinked.In one embodiment, pervious course material is pressure-sensitive adhesive, comprises Acrylic Pressure Sensitive Adhesive, organic silicon pressure-sensitive adhesive, rubber resin blend pressure-sensitive adhesive, segmented copolymer pressure-sensitive adhesive, and vinylic-ether polymer pressure-sensitive adhesive.Rubber resin blend pressure-sensitive adhesive comprises natural rubber.In one embodiment, pervious bed material is that a kind of Acrylic Pressure Sensitive Adhesive comprises pressure sensitive adhesive, organic pressure-sensitive gel, rubber pressure sensitive adhesive resin alloy, block copolymer pressure sensitive adhesives, polymkeric substance and vinyl ether pressure sensitive adhesive.Pressure sensitive adhesive comprises natural rubber, polybutadiene, polyisobutylene, styrene butadiene random copolymer, synthetic polyisoprenes rubber, and butyl rubber.Useful block copolymer pressure sensitive adhesives comprises styrene-isoprene-styrene copolymer-, styrene-butadiene-styrene, styrene-ethylene butylene-styrene multipolymer, styrene-ethylene propylene-styrene multipolymer.Be used for making ink, coating, paint, the commercially available emulsion of varnish and bonding agent and natural (without any color) material also can be used as pervious course material.The thickness of pervious course can be in the scope of 0.001mm to 0.1mm.Pervious course can have the neutralizing agent of activator.

Polyvinyl alcohol (PVA), polyvinyl acetate, partial hydrolysis polyvinyl acetate, tygon alcohol ether, cellulose derivative, as NC Nitroncellulose, cellulose acetate, acetylbutyrylcellulose, methylcellulose, ethyl cellulose, guar gum, as natural gum, starch, protein, as gelatin, can be used as pervious course

Water-soluble polymers can be used as activator, the bonding agent of tackifier and pervious course.The example of water-soluble polymers comprises: agar, agarose, amylorrhexis alginic acid, beta glucan, carboxymethyl cellulose, carragheen, cellulose ether carbohydrate gum, chitin, dammar gum, ethyl cellulose, gelatin, gellan gum, guar gum, gum arabic, ghatti gum, tragacanth, glue xanthans, hydroxyethyl cellulose, Hydroxyethyl Starch, karaya gum, locust bean gum, gum olibanum, partially hydrolyzed polyacrylamide, polyacrylamide, polyacrylic acid, poly-crotonic acid, poly-hydroxyl-2-ethyl methacrylyl acrylate, poly-hydroxyl-3-butyric acid acid, polylysine, polymethylacrylic acid, polymethyl vinyl ether, polypropylene glycol, partial hydrolysis polyvinyl acetate (PVA), polyvinyl alcohol (PVA), polymethyl vinyl ether, vinyl polyphenyl phenol, polyvinylpyrrolidone, acrylate, polyacrylic acid, polyallylamine, polyaminoacid, polyethylene/polypropylene acid, polycarboxylic-acid, polyglycol, tygon, polystyrolsulfon acid, tygon, polyvinylpyrrolidone, sodium alginate, spruce gum, tara gum, xanthans, their multipolymer, segmented copolymer, derivant, comprise the multipolymer of insoluble polymer.The bonding agent that is preferred for indicating equipment dissolve activating agent is water-soluble polymers, because when water is when the activator solvent, it can be set in whole layer and can prevent or the migration of activator is dropped to minimum, and provides the constraint to activator release.

Band indicating equipment is a kind of than the time, Time-temperature and the longer form of sterilization indicating equipment.It has whole features described here and comprises activator, indicator, binding, base material, bonding agent, different layer and other characteristics and processing.

Band indicating equipment has the patterned indicator of zebra, and it is to be interrupted indicator.

Band indicating equipment can be applicable to all objects or is only sealed in the place needing.

VELCRO provided with fastener can be by developing with that face of metallization that simultaneously scribbles in addition activator.

All indicating equipments comprise that band indicating equipment has and can revise indicative character, as created with organic silicon coating printing below indicator/metal level.

It is better that band indicating equipment is applied on the commonly sealed location point of chest.

Can be in advance in the capping of chest with a strap as metal/activator band, and bring activation by activator again while applying afterwards.Can make as the mode of envelope by other annexes.

Activation indicating equipment can be applied current band, even if in order specifically to apply and also not need again to work out or change currently used belt.

The present invention is except making band (as shown in example 10 and Figure 35), can also be made into some bands for (1) with commercially available molecule as the moise-heat sterilization of plumbous and bismuth, (2) with oxirane disinfection, (3) hydrogen peroxide and its plasma (all from this Wood of Ohio promise NAMSA company), (4) by diacetylene 4BCMU[R-C ≡ C-C ≡ C-R, wherein, R=(CH2) 4OCONH (CH2) COO (CH2) 4H] and the Time-temperature made of its partially polymerized form, temperature and radiation indicator strip, (5) by commercially available directly-heated type film (production code member TF200C gram of rel D.T., IIMAK company, Amherst, New York) band and our phosphoric acid activation band time and the time-temperature indicator band made.With above-mentioned belt sealing etui under suitable condition.But all these belts all little by little demonstrate the variation of color.

Existing equipment has thin and a highly opaque indicator layer, it becomes transparent in the time that reaction finishes, it can print (1) information in any aspect of (as aluminium lamination) or above-mentioned indicator layer in indicator layer, and other information in (2) any indicator aspect below marker.These two kinds of information can be identical or difformities, pattern, and numeral, image or bar code, if need correct alignment.These two kinds of information can be new or different information or different colours.If information is yellow and another can be any other color, as blueness, in the time that becoming transparent, indicator layer will there is green information.By two images of correct alignment, can create the optical effect of bidimensional or 3-D effect, and therefore revise the reliability of easily knowing and confirm indicator.If image is bar code, when becoming, indicator layer can make that they are not readable or vice versa when transparent or very readable.This is a species diversity, better method make bar code read or not readable or both, compare U.S. Patent number 7157048 disclosed.In the present invention, printing bar code is on different layers.

These chemical indicating equipments have equally nearly all function of time described here and Time-temperature indicating equipment and vice versa.

Because this equipment has a thin conductive metal layer, the variation of equipment, can find/monitor out the change of equipment with little and sensitive metal indicator.Because equipment is reflective, it can use CCD types of cameras and other scanners at the external reading of certain distance.

Because equipment has two belts, this equipment can be assembled into has substantially impervious releasing layer, as the release plastic sheeting between two belts.This equipment carrys out activation equipment by impermeable bed being pulled out and pressed belt.

Also can create the removable boundary line as shown in Figure 10 and 34, by adopting non-unified wedge shape pervious course between activator and indicator layer.

Time, the indicating equipment of the removable boundary line pattern of Time-temperature and sterilization has whole features described here, comprises activator, activator precursor, indicator, bonding agent, base material, different layer and other features and method.

Removable boundary line equipment has scale and/or numeral represents the extent of reaction.Also there is information and the image of a large amount of impervious formations or uniform thickness.

Removable boundary line equipment can produce a series of information, for example, remind and when take drug/medicament.The the first, the second, three ... do what etc.This can remind patient or other people that instruction in the time taking the medicine of regulation or other is done this, does that, does not do like this.In the time that prescription is more, pharmacists can apply this indicator.

Removable boundary line equipment has the top layer with form, comes by the selected part of seeing boundary line.Scale and information are equally on the top layer of equipment or other layers at equipment.

Removable boundary line equipment can be created into other indicating equipments described here, for example, steam, oxirane, oxide plasma is as hydrogen peroxide, and formaldehyde is xeothermic, temperature and radiation.

The prototype equipment of the manual manufacture as shown in Figure 10 and Figure 34 proves, the movement in boundary line is clearly and linear in time.Boundary line Linear-moving is in time these indicating equipments of difference and similar other equipment, and very useful to making these indicating equipments.Reaction and neither one indicating equipment considerably less in bibliographical information have zero-order reaction, linear in time.This is the uniqueness of this equipment.

We find, based on sterilization, the diffusion of the removable boundary line indicating equipment of TTI and other types can be created by changing the fluent material of activator/precursor and the pervious course substrate of metal level.For some equipment, as sterilization indicator, need to select suitable activator/precursor, have with material and react and can realize, as chemical vapors comprises humidity, steam, oxirane, the fluid product that hydrogen peroxide produces or dissolve activating agent/precursor and react with metal level.The dissolving of activator is capable of circulation and rely on and create removable boundary line equipment by the design of etch metal layers.Indicator strips can, by metallization infiltration substrate, have the metallization PET film of wet coating layer or other infiltration substrates, as rectangular paper.Painted/so instruction Material Addition is only visible to the movement in boundary line in activator or substrate.

Belt and other indicating equipments have an outside surface, and inside surface and first and second finishes end.So belt has some extra layers and comprises adhesive phase it can be applied on an object.Indicator layer is on the first nearest outside surface that finishes to hold of belt.Active agent layer is on the second nearest end end.Activator is to be applied on the second nearest inside surface that finishes to hold of belt.When belt is packaged on an object in advance as user's wrist strap, there is the outside surface of exposure, the first outside surface and second that finishes end finishes the inside surface stack of end and contacts with each other, preferred adhesive contact.Activator and indicator reaction are impelled the generation of visual variation.Visual variation is like this can be observable from outside surface.

Belt and other indicating equipments have an equipment, as adhesive tape, and VELCRO, the extended layer of embedded button, for further guaranteeing the integrality of belt.

The length of belt depends on object used and can grow to several meters or longer from one centimetre.

It can be as including patient name, the hand gong of patient's number or other identifying informations.

Belt has the way of amendment instruction.

Substrate for belt can be paper, weaves cotton cloth, and tatting or non-woven membrane.

Belt described here can be I.D. oolemma, time-giver band, time-temperature indicator band or sterilization band.

In some cases, this equipment can be inactivated, and for example, when acid is as activator, alkali can be used to this equipment of deactivation as ammonia.Gas can be used for deactivation as oxirane etc. sometimes.

Any design, pattern, information, image and similarly can be by printing on facial mask and with hot water, steam or activator bring non-facial mask etching metal layer is created.These processes create any design, pattern, information, picture strip, greeting card, photograph, electronic circuit and similarly than the etchant by adopting other as carried out etching with liquid acids or alkali more simply and safety.Game, toy, magic, entertainment, secret informations etc. also can create by these processes.

Report, for the energy of activation of TI and TTI equipment generally higher than 15 kcal/mol, is about 25 kcal/mol conventionally in the literature.The etching reaction energy of activation of present device is only approximately 7 kcal/mol.Produced like this indicating equipment of the present invention is highly suitable for persond eixis equipment.Energy of activation is as can be by adopting suitable infiltration or barrier layer to obtain higher than 20 kcal/mol.Thereby pervious course spreads therein by the pervious course of heterogeneity and thickness activator and makes to change needed asynchronism(-nization).

These except mentioning here, by selecting suitable indicator, as metal, the metal alloy of different metal ratio and similar (as aluminium, copper, X alloy) and activator, precursor and their potpourri, can obtain the energy of activation (Ea) from very low (a few kcal/mol) to very high (as 100 kcal/mol or higher).Character by different bonding agents or adjuvant changes energy of activation.

Can use equally the indicating equipment that has metal level on every of substrate, as there is identical or different thickness.This equipment needs two activation zones, one, every limit.This activator band can be variety classes and one deck or two-layer being activated.Therefore, this equipment has become dual indicating equipment substantially.These dual indicating equipments have every other characteristic described here.

Can use equally the indicating equipment on every of substrate with active layer.That single or double metallo-plastic film all can be applicable on each of dual activator band.This activator and indicator layer can be that variety classes and one deck or two-layer active agent layer can be activated.Therefore, this equipment has become dual indicating equipment substantially.These dual indicating equipments have every other characteristic described here.

Adopt the equipment on each of metal level with active layer can be created by sample.For band indicating equipment, active layer can be longer and narrower than active agent layer with vice versa.Activation zone can be used for current band.

RFID indicating equipment can be used for object independently or the case of a lot of objects/wrap, as perishable items is housed.It also can be used as TI, TTI and SI.RFID indicating equipment is for guest id card, and the stock control of the management of people's entrance and exit and perishable farm products is a good idea.Indicating equipment of the present invention can be applicable on RFID equipment equally.Can be used for commercially available RFID or similar equipment, as the indicating equipment on electronic time or Time-temperature instruction dress and same target.Present device equally also can be applicable on electronic time-thermometrograph.

This RFID indicating equipment also can be applicable to an object as the inside of a chest or outside.

Assembly system for RFID indicating equipment can be two roll-good form, and one of them is that RFID inlay is activator band with another.

We of RFID indicating equipment inlay or it does not need each part with diaphragm to be coated with matcoveredn, as etching facial mask.

Here there is a chip and be much etched in variety classes on same antenna, the different antennae of thickness and the activation zone containing the different-thickness of wedge shape activator.RFID indicating equipment has one of them antenna and two chips that obtain by etching method.

RFID indicating equipment write with read aspect substantially the same with common RFID.Available identical software and equipment.The conventional composition that all RFID are involved, equipment and writing, reads with the method for report information and includes scope of the present invention in.

Here there is more than one RFID and be used in a RFID indicating equipment on object.

The equipment for etching RFID antenna that the present invention reported here can be used to create or destroy the circuit of a lot of electronic equipments.

Be printed on circuit board, RFID, the circuit on EAS and similar devices described here has more than one electronic chip or element, is used for monitoring different parameters, as the time, Time-temperature and described factor simultaneously here.

Other all equipment described here can have RFID equipment equally.

Other demonstration equipments can be connected to RFID demonstrates the variation of electric conductivity.

Cheap RFID label can be created by technology described here and by creating electronic chip from organic semiconductor machine material.

The iron oxide by dissolving with the magnetic recording tape of activator makes magnetic recording tape inactivation make similar RFID.

The present invention's a kind of very thin metal conducting layer that also leads, it is by vapour deposition or at polymeric membrane substrate or be coated with the metallic film sputter of touching or print with activator that can etching metal and form.Printing activator is the form with electronic circuit pattern.Polymeric membrane substrate is by any plastics, preferably the polymkeric substance of epoxy radicals.

Preferably, polymeric membrane, by a kind of pliable and tough, has good anti-tear pulling and chemical stabilizing material composition.This polymeric membrane is born temperature more than certain environment.Preferably, polymeric membrane is by a kind of material with low water absorbable and dissolvent residual.

Be applicable to polymeric membrane of the invention process and comprise dacron, as polyethylene terephthalate, polybutylene terephthalate and Polyethylene Naphthalate, polypropylene, polyvinyl fluoride, polyimide, nylon and their multipolymer.Be applicable to other polymeric materials of the present invention and include, but is not limited to phenolic aldehyde or dicy-curing agent, cyanate, bismaleimides, the epoxy resin cure system of polyimide.

Be applicable to metal of the invention process and comprise zinc, indium, tin, cobalt, aluminium, chromium, nickel, nickel chromium triangle, brass, bronze or their alloy.Other applicable metals comprise magnesium, titanium, manganese, bismuth, molybdenum, silver, gold, tungsten, zirconium, antimony and their alloy.

Polymer layer for metal and protective seam at least comprises a suitable thermoplastic polymer.These layers can be formed by identical material, or are formed by different materials.The object lesson of suitable thermoplastic polymer comprises, tygon, polystyrene, polycarbonate, polyethylene terephthalate, different ethylene glycol polyethylene terephthalate, Polyvinylchloride, thermoplastic polyurethane, acronitrile-butadiene-styrene, polymethylmethacrylate, polypropylene, polyvinyl fluoride, PEN, polymethylpentene, polyimide, polyetherimide, polyetheretherketone, polysulfones, polyethersulfone, ethene chlorotrifluoroethylene, cellulose acetate, acetylbutyrylcellulose, plasticised polyvinyl chloride, polyester-polycarbonate blend, Ionomer, co-extrusion film or list etc. with these thermoplasticss.Thermoplastic polymer can be flexible thermoplastics, and is commonly called thermoplastic elastomer.

Comprise for the circuit of EAS system antenna and can adopt the same or similar equipment for RFID and other electronic equipments described here, molecule and method are created, and are included on the two sides of suitable substrate and create suitable circuit.

EAS described here or security system can be used for calibrating and prevent that stealing and/or retailer or other places from taking out without approval as the articles for use in library or commodity.EAS equipment or eas tag are to be attached to, and contacting, or method for distinguishing are firmly bonded on articles for use or the commodity of protecting or its packing box.EAS can be a lot of different specifications, shape and form, and it depends on the type of particular safety system used, type and the specification etc. of articles for use.

Theme safety label of the present invention can be designed for the electronic safety system of the interference identification of radio frequency (RF) electromagnetic field.Such electronic safety system is generally to control articles for use when place and must permit defining of the passway passed through in control area, to set up electromagnetic field to leave at one.Can produce the tag circuit echoing and be attached on every articles for use, the tag circuit of existence indicates identification articles for use to take out without approval by receiving system in control area.Make tag circuit inactivation by authorized person, off resonance or remove and any mandate articles for use are left only have article to allow to activate from having the place of passing through controlling alarm region.

As microwave burning and the thin metal layer that breaks, for RFID, circuit, pattern, design, the design of printing etc. can be created by the radiation with microwave selective optionally equally.

Replace circuit and other patterns, can be by have facial mask type ink (using ink-jet printer) or metallized substrate on print the prefabricated printing board material compacting of required image or remove when bring etching then when complete etching with activator after activator band tonne.Also can create hydrophobicity and hydrophilic area by selective etch.

Activator band or activator coating can be used for etching metal classification as silk, sheet, piece, pot, the title on container and instrument or other information.Then application activator band is removed on mark/facial mask with information when etching completes.The type of etchant and concentration depend on metal and alloy.Similar belt can be used for etching ceramic/glass and plastics, for example, and by sodium fluoride and sour reaction, by applying the second band/coating of the second precursor of generation etchant after application first precursor band/coating.This will reduce to greatest extent harm and make process simple.The belt that application contains phosphoric acid, nitrous acid/nitric acid of producing subsequently by sodium nitrite/sodium nitrate carrys out etching metal.

This process also can be by optionally anti-environment metal and alloy etch are created small-sized and large-scale mark and plank.

The place that steam sterilization disclosed herein is activator at reactant is main or direct equipment.

Moise-heat sterilization indicating equipment for TI and TTI described here is identical.But, moise-heat sterilization indicating equipment do not need activator or activator band in free because water is exactly activator.Therefore, metal plastic film can be used as a moise-heat sterilization indicating equipment.

Moise-heat sterilization indicating equipment has all fundamental propertys described here and comprises activator, indicator, binding, base material, bonding agent, different layer and other characteristics.

A multicycle sterilization indicating equipment can be developed in several ways, and as used thicker aluminium lamination, it is just to dissolve at all after dates of some.Removable boundary line is an example for multicycle indicating equipment.

Above moise-heat sterilization indicating equipment can have, below or other indicating equipments as printed with having on the face of oxirane.

Except denoted object is by the process indicating equipment of disinfecting, by using suitable activator described here, indicator, equipment and method are created more eurypalynous indicating equipment, integrator and simulator.

Equations of The Second Kind: for the indicator of fc-specific test FC process.Remove test for the air of vacuum and steam sterilizer and belong to this class.These indicators can only be determined air or the gas in the efficiency of vacuum pump and steam, revealed.Their are indicated the efficiency of air purge system but are not the effects of sterilization.Because the etching of metal is depended on equally existence or at the air for oxidation and the steam condensate (SC) that exist, can be developed Equations of The Second Kind indicating equipment.

The 3rd class: one-parameter indicating equipment.These indicating equipments are designed to respond a key parameter as temperature.The 3rd common class indicating equipment is glass temperature pipe, contains a kind of chemical substance of dissolving or change color in the time reaching minimum temperature.These indicating equipments can not be indicated the T.T. under a temperature or excessive temperature.Whether the temperature that they can be used to be determined at huge parcel center is suitable.By select the suitable activator dissolving at required temperature, can develop the 3rd class indicating equipment.

These indicating equipments are in order to respond a crucial parameter, as temperature sterilization.The common type of one 3 kinds of class indicating equipments is a kind of chemical substance in a glass temperature pipe, and fusing and change color are worked as minimum temperature and reached.These indicating equipments are not presented at a temperature or whether temperature exceedes T.T..They are used to determine whether realize at suitable temperature Shi great Bao center.The temperature needing by selection, in the thawing of a suitable activator, can be manufactured 3 grades of indicating equipments.

The 4th class: multiparameter indicating equipment.The parameter and standard value that these indicating equipments are designed to select two sterilization key parameters in a disinfection cycle responds.An example of this class indicating equipment is to contain when being exposed to the lower variable color ink of the correct combination of sterilization parameter.Because time and temperature or temperature and steam (or other sanitizers) are depended in the etching of metal equally, can be by optionally suitable two activators and indicator are developed the 4th class indicating equipment.

The 5th class: indicating equipment/integrator to two or more parameter sensitivities and with 15% anticipatory goal response.In this classification, change color must be suddenly, do not reach within the scope of 1 DEG C if occur in 15% re-set target neutralization target temperature, and variable color must not occur.For example, indicating equipment accept (agree to or pass through) 4 minutes at 132 DEG C just must refusal (ignorance) at 131 DEG C 3 points 22 seconds.Because the time is depended in the etching of metal equally, temperature, steam (with other sanitizers) and have the removable boundary line equipment of vigorous reaction phase, can be by optionally suitable two activators and indicator are developed the 5th class indicating equipment.

The 6th class: two or more parameters of indicating equipment/integrated sensitivity and with 6% anticipatory goal response.In this classification, change color must be suddenly, do not reach within the scope of 1 DEG C if occur in 6% re-set target neutralization target temperature, and variable color must not occur.For example, indicating equipment accept (agree to or pass through) 4 minutes at 132 DEG C just must refusal (ignorance) at 131 DEG C 3 points 45 seconds.Because the time is depended in the etching of metal equally, temperature, steam (with other sanitizers) and have the removable boundary line equipment of vigorous reaction phase, can be by optionally suitable two activators and indicator are developed the 6th class indicating equipment.

Similarly for other disinfecting process as oxirane, plasma, formaldehyde, xeothermic and polymorphic type indicating equipment/integrator radiation can be by using the activator of the described here equipment that is used to indicate, indicator, equipment and method are made.

We notice on metal level, there is condensate water if the dissolving of the aluminium of thin aluminium lamination becomes time delay.Therefore, by adopting metal plastic film or those have water instead of dry steam is wettable, dissolve, the specific coatings of oedema is made the equipment as Bao Yi-Di Ke.On metal level, the patterned coatings of penetration material can be used as Bao Yi-Di Ke equipment.If there is the condensate water in moise-heat sterilization process, metal part will can be not etched.

Except using continuous gold-plating plastic sheeting, the inner liner metal plastic sheeting that also can make good use of designs, ruling.

Water color ink can coating prevent from tarnishing and react with activator, but at high temperature it can melt dissolving and therefore can be used for moise-heat sterilization indicating equipment.For water-based metal powder, activator is water insoluble, and vice versa.

Reaction does not need metal powder to dissolve completely, as long as it tarnishes by activator.

Nano-scale with respect to huge thin sheet of metal particle.

Xeothermic indicating equipment comprises dry heat sterilization indicating equipment, by selectivity suitable for sterilize or similar procedure or lower than xeothermic temperature under melt etchant and create.Matrix must be heat melt bonding agent as PSA or just scribble activator without clinging power resin.Non-adhesive matrix is the first-selection of xeothermic indicating equipment.Melting activator can etching metal/indicator.These equipment can be used as microwave and boil indicating equipment, especially in the time that metal level is very thin.

Polyvinylchloride (PVC), polyvinylidene chloride (PVDC), halogenated polyolefin and other halogen polymers and multipolymer thereof are suitable as the activator for xeothermic indicating equipment.For example, contain aluminium, zinc, the PVDC coating of the particulate of copper and alloy thereof is in the time being heated to 160 DEG C, and they experience the variation of transparency, as reacting by hydrochloric acid (being produced by halid thermal decomposition) and metal.Other adjuvants, activator, activator and catalyst precarsor can be used for changing reaction rate.

Salt, particularly strong acid is if sulfonic acid and amine are as primary amine especially long-chain, can be melted in temperature required under, also can be used for manufacturing xeothermic or temperature indicating equipment.

Activator also can microcapsules.Microcapsules can or lower than 160 DEG C at break for the monitoring of dry heat sterilization.

Ink or coating molecule by metal as aluminium and alloy thereof, binding, medium and reactant are as acid, alkali, salt or oxygenant (comprising their precursor) composition, has with said metal or can be used as the ability that indicating equipment disclosed herein reacts as the on-chip dry coating of steam sterilization.Reactant and metal react and tarnish or be completely dissolved.Also can in said ink or coating, add dyestuff or pigment.The dyestuff adding or pigment can or cannot experience with steam the variable color of color.For example, in the time that auramine-0 joins in the silver-colored ink of aluminium, its occurs golden.In the time of steam treatment, auramine-0 becomes colourless and gilt and becomes silvery white.Some dyestuffs and pigment can experience the variation of color, and as guinea green B when the steam treatment, alkali blue 66 and alkali blue 41 become redness, then substantially become colourless, therefore they and similarly other dyestuffs and pigment can be used to obtain with steam other color.Therefore, dyestuff and pigment, they change color and whether can join in moise-heat sterilization indicating equipment.

Activator for steam and other indicating equipment can be water-insoluble water-based inks and the insoluble solvent-based ink of solvent.

By adding suitable activator and/or precursor in metal ink (ink has the particulate of metal or alloy), can make other different instruction ink.For example, in metal ink, can create the thermocolour ink for different temperatures by adding temperature-activated agent/precursor.Same, can create for some other processes as the time, Time-temperature, pressure, radiation, and raw material is as moisture, chemicals, the ink of chemistry and biological agent.

The involved in the present invention binding system that is used to indicate potpourri can comprise into membrane carrier, and in order to obtain gratifying variation under moise-heat sterilization condition, it is permeable steam and other sanitizers crossed.Preferably, binding system provides has film forming characteristics, and object cohesive is good, and the moise-heat sterilization of heat resistanceheat resistant and moisture and other indicating equipments.Preferred ink of the present invention comprises binding.This binding can comprise any water resistant, heat resistanceheat resistant polymkeric substance.Applicable polymkeric substance comprises that soluble polymeric thing is as ethyl and NC Nitroncellulose, cellulose acetate and derivant thereof, hydroxypropyl cellulose, polystyrene, polymethylacrylic acid, Polyvinylchloride, polyvinyl acetate (PVA); Emulsion latex is as polyvinylidene chloride, acryl resin and polyvinyl acetate; Cross-linked resin is as P-F, urea-aldehyde and carbamide; Tygon, polypropylene, polyurethane, dacron, polycarbonate, polybutylene, tygon butyraldehyde, polybutadiene, and their multipolymer, ultraviolet (UV) curing systems; And drying oil.

The ink of one aspect of the present invention, comprises the aqueous dispersion of metallic pigments and film-forming resin.Metallic pigments can paillon foil (being generally flakelet) and non-foil-type.Preferably, metallic pigments are to include aluminium from one group, copper, bronze, their oxide, the metallic pigments that choose in their anodic oxidation (provide while completing and dodge look) and above-mentioned any combination.The definition of metallic pigments comprises other glossiness things, and the appearance that it can provide metal or dodge look, as the honorable agent of pearl (as bismoclite (BiOCl)), can be used for except a little or replaces metallic pigments.

Although larger metal particle can be used for application disclosed herein, preferred, its size is less than in 15 microns and approximately 2 to 15 micrometer ranges.Preferred metallic pigments comprise the ink of approximately 2% weight to approximately 30% weight range, are preferably approximately 5% weight to approximately 10% weight.

Suitable film-forming resin also comprises water soluble resin, as hydantoins-copolyoxymethylenes, as dimethyl hydantion-formaldehyde (DMHF) and 5,5-dimethyl hydantion yuban (also referred to as 5,5-dimethyl-2,4-imidazoles).Preferred dimethyl hydantoin-formaldehyde film-forming resin.Other resins for ink of the present invention comprise polyvinyl alcohol (PVA) and water-borne polyether polyols with reduced unsaturation.Preferred film-forming resin comprises the ink of approximately 10% weight to approximately 70% weight range, is preferably approximately 30% weight to approximately 50% weight.

Add the antisettling agent of minute quantity.Contribute to the stability of ink.Preferably, about 0.001% weight of the scope of the antisettling agent in ink is to approximately 0.11% weight.The antisettling agent being preferably used in ink is natural gum, as xanthans natural gum.

Preferably in ink molecules, add antiseptic (as fungicide and/or germifuge).An example of antiseptic is 1,2-benzisothiazole-3-ketone, and its scope is that about 0.05% weight is to about 0.15% weight.

Disclosed equipment here, can be by being applied in activator in ultraviolet curing binding or the coating of activator precursor, and it can be by solidifying as ultraviolet ray with radiation.Can protect the activator coating under environmental conditions with extra protective seam.Activator, precursor, binding, the needed application of equipment is depended in the selection of hardening agent and any adjuvant.For example, manufacture moisture indicator, UV can be solidified to five phosphorous oxide in binding, be coated in infiltration water steam on metallo-plastic film.In the time being exposed in water, becoming very moisture absorption five phosphorous oxide and react production phosphoric acid etch metal layers with water.

This ultraviolet curing Method type be here disclosed equipment preferably select manufacture method because the method is quick.

Binding should may penetrate into raw material for processing as steam, oxirane, hydrogen peroxide, formaldehyde etc.

Active agent layer have super nanometer to the raw material of micron particles as zinc paste, titania, microcrystalline cellulose.These contribute to lip-deep reaction even.

Antioxidant, as butylated hydroxy anisole and dibutyl hydroxy toluene (BHT) can add, reduces oxidation.

NMF, as propylene glycol, hypersorption polymkeric substance, sorbierite and lactic acid can be added in active agent layer, prevent equipment desiccation described here.

For many application, if steam indicating equipment or water are as a key element or affect the indicator of its performance, preferably water insoluble resin in dry or heating, self-crosslinking glue, latex, resin solution.

Microwave boils indicating equipment and has a lot of common characteristics of every other equipment disclosed herein.

Although a lot of design disclosed herein, the microwave that formula and method can be used as having suitable change boils indicating equipment, by being to adopt to have the very thin aluminum metal layer (in the prior art so-called pedestal) of optical density scope between 0.05 to 0.5, most preferably optical density is approximately 0.2.

Microwave boils indicating equipment can be anywhere, the inside or above, the inside of container or outside surface.These indicating equipments also can be used as a part for container or a part for heating cushion.This design is identical with the microwave susceptor of reporting in prior art.

The activator that boils indicating equipment for microwave is more dystectic compound, and its fusing point reaches temperature the etching metal wanted.Activator can be also microcapsules.

Time-temperature instruction (TTI) equipment disclosed herein can used self-heating bag, and its function is to apply the outside energy.By heat produce compound as calcium oxide and its typical case of living solution be that water produces heat.The TTI of effect self-heating bag the have relatively high expectations activator of temperature or weak activator and/or strong/resistance to or thicker indicator.Here a lot of these activators and the indicator listed can be used.Preferably the activator of higher temperature is for self-heating bag.These indicating equipments can be used on Anywhere, the inside or above, the inside of container or outside surface.

For monitoring (be iced to and the thaw) indicating equipment that thaws of the frozen goods/perishable product in freezing state and storage life, as substantially the same with the Time-temperature indicating equipment being formed with indicator strip by activator band in frozen food, and method for making is also substantially the same as described herein.Main difference is exactly the state of activator or active agent layer.Substantially be solid-state and/or not transportable/not diffusible for the activator of indicating equipment of thawing, the indicating equipment that therefore thaws be applied in when article are freezing states.The indicator strip of indicator strip and Time-temperature is basic identical, as contained the thin layer of activator on substrate.Bring and manufacture freezing indicating equipment by application instruction from above agent band and activator.

By adding coactivator, it is different that salt or solvent make the desired transparency change of temperature and time temperature.

The indicating equipment that thaws can scribble by making (1) layer of indicator strip, it is when becoming while contact totally with metal level or the water or the water vapour that are printed with on the layer of any information, and the activation that (2) scribble water base binding local desiccation brings creation.Thaw indicating equipment by be applied on indicator and freezing point under activator bring creation.If equipment is taken to temperature above freezing, the ice of glue the inside by melt and slowly then make to become clean to opaque layer diffusion.Therefore make to be hidden in metal level below or the information of printing and become visible.Indicator strip can have available water and dissolve the also activator of etch metal layers.

The indicating equipment that thaws also can be developed by fine metal particle and the activating mixtures that can melt also dissolution of metals particle slowly at 0 DEG C.It is better for this system that UV solidifies binding.Low temperature (lower than 0 DEG C, as-40 DEG C) indicating equipment can be by selecting the suitable activator with low melting point like this to develop.

The indicating equipment that thaws can be prepared in advance, for example, by scribble microcapsules on metallo-plastic film, microcapsules rupture discharge etchant/activator when freezing.Core material, as activator and etchant and film/outer wall raw material must select to be suitable for the microcapsules for the preparation of the indicating equipment that thaws.There are the microcapsules that can break and discharge the activator in it time above freezing by selecting suitable microcapsules raw material and method can be made into.

Here some listed activators can be used as the indicating equipment that thaws.Can use water-soluble and not hybrid activator of water.Liquid activating agent is not mixed with water but can be surrounded with water.Preferred is water for the solvent of activator.The cosolvent or the chemical agent that are used for the freezing point that changes water can be used as changing needed freezing point temperature.Preferred cosolvent is water miscible agent.

The indicating equipment that thaws postpones the required time that is provided for color change and many other Time-temperature characteristics described here.

The potpourri of available two kinds of dissimilar microcapsules, for example, when being cooled to default lower time of low temperature, contains a kind of activator or solvent that is not frozen into solid, but contains another kind and be frozen into activator or the solvent of solid.

When turning cold, lower activator does not need to be frozen into solid.If activator is not frozen into solid and have some vapour pressures or volatile grade, can and cause variation with metal reaction equally.

Once activator is released, equipment has just become Time-temperature indicating equipment.Variation in the following transparency of freezing point temperature is faster.Between frost free period, etching also changes color, and is used as the indicating equipment that thaws.Therefore, by selecting suitable activator, solvent, cosolvent or their potpourri, can be used to develop the indicating equipment that freezes or thaw.

Microencapsulation activator dispersibles at binding, comprises contact adhesive and is applied on metallo-plastic film.Can previously prepared binding by UV curing monomer and/or oligomer, therefore they are easy to the coating of not breaking.

Can with any similar equipment maybe can control activator discharge approach replace microcapsules.

Also can use activator or the solvent of can be separated (for example, United States Patent (USP) 6472214 is described) and etch metal layers.

These thawing equipments are all solid state and micro-indicating equipment that freezes substantially.

These temperature indicating equipments also have nearly all characteristic of time described here and Time-temperature indicating equipment, and vice versa.

Much liquid is amplification or contraction in freezing point time.Water is exactly an example.It increases 10 in freezing point.A lot of materials, as metal and plastics, their amplification and contraction tool during heating and cooling is very different, and for example, main difference is coefficient of thermal expansion.The shallow layer of the friable material on other materials has obvious different coefficient of thermal expansion, and consequently friable material is extremely obvious.For example, not plasticized polyvinyl chloride is a kind of frangible plastic, and its coefficient of thermal expansion is 52 × 10～6/K, and the aluminium of comparing is 23 × 10～6/K.Dye solvent can be by the significant change of break indicated temperature or freezing point.The coefficient of thermal expansion of water is 0.16 × 10～4/K in the time of 50 DEG C, and comparing in the time of 0 DEG C is 0.68 × 10～4/K.

Same, the binding that contains dyestuff, as the contact adhesive that contains water (hydration pressure-sensitive adhesion agent molecule as dry in part), can be applicable on the thin layer of binding material especially opaque adhesion-layer materials.In freezing point (as more than 0 DEG C) thus water part that amplification is made to be bonded in the bonding agent on frangible layer break with thin frangible layer.Coloured water on melting point is indicated freezing point by diffusion.If the part of dry adhesion thing has uncongealable color liquid and can be spread and be indicated freezing point by crack in the time being in frozen state.

Also can make thawing equipment with the coloured water of the microcapsules that are surrounded by activator.Also can discharge activator by the disclosed phase splitting technology of U.S. Patent number 6472214.

Can be on the substrate of equipment type information or image and the disclosed molecule of U.S. Patent number 7343872 and similar molecule become clean from opaque.When disclosed diffusion molecule is in freezing point in those patents, become suitable clean or transparent.Can make the emulsion of two kinds of liquid, as water, toluene.This latex or emulsion are single composition and without any the adjuvant of kind or the nano particle simply forming for nucleus or have jade-green dyestuff and red background, therefore melt light green color when him and become more shallow and then have the more shiny red that information " freezes " and occur.This information can be any.

Freeze indicator strip and be included in United States Patent (USP) #6472214 and 7343872 disclosed equipment, molecule and method, or available devices on any market, as comprise those those of thermal instrument company of the U.S. of Dayton city, visible Ohio equipment based on microcapsules rupture on market.

If microcapsule wall material is by if U.S. Patent number 6602594,4729671 and 4643588 disclosed materials are as aliphatic chain, wax and other compounds composition, can create a temperature indicating equipment.

High temperature (more than 250 DEG C) indicating equipment for high temperature can, by with described here developing for freezing-thaw indicating equipment materials and methods, use the activator just melting in required temperature as passed through.

By selecting the suitable alloy that is used to indicate agent to manufacture high responsive wet steam/humidity and being used as humidity indicating equipment.Same, can manufacture oxygen indicating equipment.Metal for humidity and oxidation indicating equipment is sodium, lithium, potassium, caesium and similar and its his alloy.In humidity, in the example of steam and oxygen indicating equipment, oxygen and water are activators.The micropowder of metal can be used as drying agent as aluminium and indium.

Various metals and metal oxide, as sodium and calcium and oxide thereof, can be used as the activator precursor of moisture indicating equipment.Also can be with nonmetal moisture absorption and drying material, as acid anhydride, phosphorus and oxide thereof.P2O5, phosphorus pentoxide (and homolog) be precursor in ideal because it be very moisture absorption and react with water and produces sour (phosphoric acid) etching metal.Dissolving with fine dispersion coating of phosphorus pentoxide on metal level can be used as humidity indicating equipment.

Phosphorus oxychloride (POCI3) reacts with water and generates hydrochloric acid.Phosphorus pentachloride and phosphorus trichloride (PCI5 and the PCI3) acid of its generation can be used as the precursor of the activator for monitoring moisture and humidity.These materials can microencapsulation.Same, under higher temperature, decompose the indicator that acidic halogenide can be used as other and comprise sterilization, especially moise-heat sterilization.

Humidity indicator can be as the wet indicator of diaper.

Then the methanol solution that contains p-toluenesulfonic acid that can scribble by scribbling polyoxyethylene for the activator of humidity indicating equipment on dacron release film on teflon is done and is created at the drying box of 80 DEG C.Humidity indicating equipment is by being applied in the dry coating of metallized polyester film and removing release liner and create.This equipment is exposed under ambient humidity, light and temperature (about 80%).This metal level dissolved at about 2 hours.

Oxygen scavenger, absorber, the reactant that maybe can produce activator can be used for opening time and the Time-temperature monitoring after container.

Etching metal alloy can be used for the monitoring to opening the surrounding environment after container as aldary (when being exposed to surrounding environment etching of lower time tin or zinc and staying and become black at the back side of copper).Micropore metal and or microparticle metal and air/oxygen and/or water be oxidized/react and can be used to monitor the air time of opening after container.

White and yellow phosphorus is sent out with oxygen but can not be generated phosphorous oxide with aquatic reaction, and it reacts the phosphoric acid that generates activator with water/moisture.Therefore, white or yellow phosphorus, as shallow layer or microencapsulation, can be used for monitoring and opens the time after container.The oxidation reactant that can generate activator can be used for these application.

When thin metal layer is sterilized indicator as supervision, this equipment has the nearly all characteristic of Time-temperature indicating equipment described here, and vice versa.Sterilization indicating equipment and time and Time-temperature indicating equipment described here have essentially identical design, shape, and size, color, pattern, numeral, figure, image or bar code, and experience essentially identical variation, vice versa.Having some according to application changes accordingly.

Analyzer described here, what display and indicating equipment mainly presented is the indicating equipment of two dimensional form.Use activator described here/disclosed, indicator and binding, and can manufacture three-dimensional indicating equipment by the thicker layer of preparation.Three-dimensional measurement device for ionising radiation can be manufactured by materials and methods described here.Polymeric material and the activator/precursor with Nanoparticle metal can be manufactured 3D analyzer.This equipment also can be manufactured by the indicator of alternate multiple and activator/precursor.

Know loss indicating equipment at prior art file in as U.S. Patent number #7267880, also can be by manufacturing loss indicating equipment with materials and methods described here.Loss indicating equipment comprises friction, and wearing and tearing, grind, and damage and use/abandon indicating equipment.A lot of equipment, as shaver be done for or after certain operating period not recommendation or damaged.Information or color are printed under metal or opaque coating.After certain operating period, information and color that this instruction opaque layer/metal level has lost and printed by below are indicated explanation.

No matter be metal, shallow layer, narrow, fiber, film, the form of hologram and similar can be used in security system, the present invention can be used for calibrating and forges, and distorts and/or whether recognition system is legal, comprises the impact of monitoring age and environmental baseline.A lot of bank note has metal fibre or narrow.Available activator System Coating on metal covering.The characteristic of activator depends on metal and purposes.Can there be printing on metal and/or activator surface.Can be on active agent layer or below print.Disclosed invention here also can be used for coin.

Controlled release system, as the microcapsules known in the art, can be used for controlling the release of activator.The pressure-sensitive adhesion glue with activator is exactly a controlled release system, and therefore any other controlled release durg delivery system can use on active agent layer or activator band.

Activator can microencapsulation.This equipment can be by exerting pressure or activating by the fusing microcapsules that break.

Controlled-release technology is applied in the release field of control many kinds of substance allowable.Because activator has the ability of dissolving some metal as water and oxygen, technology disclosed herein can be used for controlling the release of the multiple article with metallic coating, comprises medicine, food and agricultural application, agricultural chemicals, cosmetics and household products.Select suitable metal or its alloy to depend on material and application.By selecting suitable metal and thickness to manufacture to allow medicine, food and agricultural application, agricultural chemicals, the sustained release of cosmetics and household products, slowly discharges, and discharges for a long time or time controlled released, controls and discharges or continuous release.Activator can add or environment be exactly activator as body fluid, water.Thin metal layer in the control releasing arrangement providing is for encapsulation, covers, and the dissolving of passing through said metal of Protective substances discharges.

Due to water and the very thin metal level of salt dissolving, therefore can be used for controlling medicine, food and agricultural application, agricultural chemicals, the release of cosmetics and household products.

Control releasing arrangement and can be and there is thin metal layer or other shapes as at least thering is the granule of flat-panel devices of a thin metal layer.

Many indicating equipments described here can be by scribbling the suitable activators having for preparing microcapsules, and the microcapsules manufacture of indicator and materials and methods forms.For moise-heat sterilization indicating equipment, select microcapsules under needed temperature and humidity/steam, to discharge activator or color material.Can control the indicating equipment of activator and other materials release by controlling the release manufacture of activator and other microencapsulation materials.

There are a lot of different direct heat to print, break or activated material method can be used to manufacture a variety of equipment and the described here method that is used as indicator and activator metal.This equipment is by manufacturing with the microcapsules that contain activator, as phosphoric acid and/or by metal level and metallic particles coating.In these equipment,

(1) activator and indicator are all in the identical faces of substrate, as by scribble one deck activator microcapsules on metal level, (2) metal level in one side and activator microcapsules at the another side of substrate, (3) metal level is on a substrate, and microcapsules are on another substrate, and by they manufacturing equipments that connects together.

Can have the available color layers of extra tradition (multilayer) to develop microcapsules, therefore needed information can print.

The metal plastic film in one side with hot print ability coating can be used to use thermal-sensitive printer printing information.Same, the metal plastic film in one side with direct heat print capacity coating comes type information and other guide and can manufacture to scribble one deck and contain activator as the microencapsulation coating of phosphoric acid, and can print and activate this equipment with thermal printer.

Adopt direct thermal printing technique, more easily create " not sterilization " two information to " sterilizing ".This can scribble a bulk by the molecule with direct heat print capacity on indicator.In bulk, print a part of information (as " not ") with thermal printer.Bulk comprises that vocabulary " not " becomes black in the time of heating or boiling to 70 DEG C or higher (depending on the character of direct heat coating).By controlling and select suitable material, can manufacture and become black when bulk after effect product sterilization.Therefore, after sterilization, only has the vocabulary appearance of having sterilized.In addition, vocabulary " not " can be printed on top and film metal below " not ".So direct heat susceptible coating, microcapsules maybe can not be used for monitoring sterilization.

Except the printing of direct heat printing technique/molecule, can use other similar printing technology/molecules.

Can write by a kind of color " not sterilization " and also scribble a bulk with same color at the back side of metallized film, in the time that equipment/product is sterilized, so because same color vocabulary " not " be can't see, vocabulary sterilization is to write on facial mask.

Information can be printed by any language or any shape.Information also can be used to create know marking device and or method use, as, before going out before processing " end ", " boiling ", " plasma " and appearance " processing finishes " after process/sterilization, " sterilization finishes ", " boiling processing ", " moise-heat sterilization ", " plasma treatment " or " plasma ion disinfection ".The type of these information can be used and identify process.

Information can be printed with metal ink printing and activator.When sterilization, because causing information, corrosion of metal disappears.

Directly temperature-sensitive printable layer can be in any position of equipment.But, optimum position be from the teeth outwards or equipment surface approach that layer on.

Thermochromic material variable color in the time of heating, variable color while comprising those fusings, can be used for manufacturing heat-sensitive paper.Can be used for direct printing with adding thermochromism that light and heat print or activate and photochromic film and paper.

Here can with the example of leuco dye comprise: (a) the colourless matrix dyestuff of triphenylmethane, as 3,3-bis-(to dimethylamino)-phthalein, 3,3-bis-(to dimethylamino)-6-Dimethylaminobenzene peptide (crystal violet lactone), 3, the amino phthalide of 3-bis-(to dimethylamino)-6-second two bases, two (to the dimethylamino)-6-isobenzofuranones of 3,3-, with 3,3-bis-(to dibutylamine phenyl)-phthalein; (b) the colourless matrix dyestuff of fluorane, as S-cyclohexylamine-β-chloro fluorane, 3-(N, N-lignocaine)-5-methyl-7-(N, N-dibenzyl amino) fluorane, 3-dimethylamino-5,7-dimethyl fluorane and 3-lignocaine-7-methyl fluoran; (c) mix fluoran dyes, as 3-lignocaine-6-methyl-7-chloro fluorane, 3-pyrrolidine-6-methyl-7-anilino fluorane, 2-[3, two (lignocaine)-9-(0-chloroanilino) the benzoyl oxide lactams of 6-]; (d) lactone compound, as 3-(2 '-hydroxyl-4 '-diformazan aminophenyl)-3-(2 '-methoxyl-5 '-chlorphenyl) phthalide, 3-(2 '-hydroxyl-4 '-diformazan aminophenyl)-3-(2 '-methoxyl-5 '-nitro) phthalide, 3-(2 ' hydroxyl-4 '-diethyl amino phenyl)-3-(2 '-methoxyl-5-methyl) phthalide, 3-(2 '-methoxyl-4 '-diethyl amino phenyl)-3-(2 '-hydroxyl-4 '-chlorine 5 '-aminomethyl phenyl) phthalide.

The example of suitable developer is phenolic compound, organic acid or its slaine and hydroxybenzoate, as phenolic compound comprises 4,4 '-isopropyl-bis-phenol (bisphenol-A), p-t-butyl phenol, 2-4-dinitrophenol dinitrophenolate, 3,4-Dichlorophenol, p-phenyl phenol, 4,4 '-cyclohexylene biphenol.Available organic acid and the example of its slaine comprise 3-tert-butyl salicylic acid, 3,5-tert-butyl salicylic acid, 5-a-methylbenzyl salicylic acid and its zinc, lead, aluminium, magnesium or nickel salt.

Emulsion or temperature-sensitive promoter can be used as color density that recording materials of the present invention provide to obtain image.Some general emulsion are suitable fatty acid amide compounds, as acetamide, stearic amide, linolenic acid acid amides, acid amides lauric acid, myristic acid acid amides, methylol compound or above-mentioned fatty acid amino-compound, if methylene acid amides (stearic amide) and ethylenediamine (stearic amide) and parabens compound are as methyl p-hydroxybenzoate, propylparaben, p-Hydroxybenzoic acid isopropyl ester, benzyl p-hydroxybenzoate.

Encapsulating material can contain colored binder, color developer, emulsion and colour or Chinese white, with in direct heat-sensitive paper and film, find the same.

Activator is as microencapsulation solid and the solution of phosphoric acid and phosphorous acid, the activator discharging while can be used as needing.Phosphoric acid (73 DEG C of fusing points) and the phosphorous acid (43 DEG C of fusing points) with low melting point contribute to encapsulation.Preferred outer wall materials is these encapsulating materials for direct heat-sensitive paper.

Contain activator for the microcapsules outer wall materials of hot print and can be used to manufacture outer wall materials as phosphoric acid, as a fatty streptamine (generation, two generations and three generations, as lauryl amine), aliphatic chain ammonium hydroxide (as TBAH), fatty acid, wax is as candle wax, paraffin and beeswax, unsaturated and crosslinkable arrives the cross-linked polymer of needed degree.

In order to prevent that harmful effect and/or unnecessary premature reaction from appearring in activator and/or indicator, can adopt protective material to carry out coating protection.Protective material should be hyposmosis or high barrier material, normally polymkeric substance or oligomer.In order to control reacting of activator and indicator, can encapsulate respectively them.Encapsulating material is commonly referred to outer wall materials.

Similar direct heat is printed coating, and coating can be made into encapsulation activator, indicator, their precursor, penetration material, barrier material, catalyzer and/or adjuvant.Can there is polytype microcapsule formulations containing different kind of material.Coating can encapsulate all or a kind of reactant.Application is depended in the selection of material.Indicating equipment can be by warm before application by these, pressure, and the material that solvent etc. activate manufactures.Along with the time, Time-temperature, sterilization and other treatment conditions, will there is certain variation in marker or part.

Any equipment that is suitable for activating by heat energy the recording materials of indication compound in recording materials that direct thermal imaging equipment can be used for quoting here.Direct heat is printed in image forming material handbook has generality to describe, and 1991, editor Arthur S Dai Mengde (Marcel De Keer, New York).

Directly thermal printing provides on request, online and customizing print and activation equipment.The information of any language side and shape all can print.Organization names, user, on the date, the information of mark and any other is required/want all can print at needs.

Equipment can activate by the method for physics or chemistry, equipment pot life (control and discharge), temperature, pressure, laser, water/steam/moisture, solvent, reagent (as Hydrogen Peroxide Disinfectant), ultrasound wave etc. activate, and depend on character and design and the purposes of equipment.Equipment also can be by ink ejecting method as being ejected into activator/solvent/chemical reagent on activator and activating, and vice versa.

Except apply activator band and other method of the present invention on indicator strip, can also activate equipment of the present invention by many other methods.They comprise following method:

A separation layer can be isolated activator well, but can be by mechanically, heatedly or similar approach ground fusing or break, and opens passage for activator, makes the equipment of activator described in being used for activating.

Microcapsules can partly or entirely be activated.The coating of encapsulating material also can partly or entirely be activated.

Can there is more than one microcapsule layer, wherein each character, function and characteristic can be identical or different.

Encapsulating material also can be released under the condition of controlling, and for example, controls activator and discharges.

Having many different modes can prepare and activate the described equipment that contains microcapsules, is some examples below:

Method 1 (Figure 28): the plastic side at metallo-plastic film forms a psa layer and a release liner (not shown) [Figure 28 (a)].On metal level, form a hot coating and/or mechanical destructible micro-capsule, this micro-capsule contains a kind of as the activator of phosphoric acid and a kind of binding [Figure 28 (b)].Can optionally on described microcapsule layer, form a protective finish [Figure 28 (c)].Can use a kind of thermal printer, an information or image [Figure 28 (d)] are write or printed to the method for infrared laser or machinery.These equipment also can be realized activation through a heating system, as warm-up mill or infrared laser.Microcapsules can break and discharge activator/phosphoric acid.An image can manifest, as the white/translucent transparent/metal [Figure 28 (e)] that becomes.Mobile from behind release liner, and the equipment after activation is applied to as perishables, on medical supplies or visitor's etc. object.D/d activator/phosphoric acid can corroding metal layer.After metal is eroded completely, an information and/or the color being imprinted on below can manifest [Figure 28 (f)].

Method 2 (Figure 30): form a printable surface on a metallo-plastic film.Use and contain activator (as phosphoric acid) on as the metal level of half, and optionally contain the pressure sensitive adhesive [Figure 30 (a)] of a kind of coloured dyestuff or pigment (as redness).On psa layer, use a release liner [Figure 30 (b)].Activator can dissolve the metal level under it, makes the activator part of metallo-plastic film become transparent [Figure 30 (b)].In the type information (as expired or visitor's as required photo) below of printable film, as on second half metal level [Figure 30 (c)].Remove release liner from active agent layer, along the middle folding apparatus of equipment, and exert pressure and make PSA can contact equably [Figure 30 (d)] with metal level.Photo and information can be after activation the top of equipment.When equipment expired (metal level is dissolved), the information of a coloured and/or printing, as redness, " X ", meetings such as " inefficacies " manifests [Figure 30 (e)] under photo.These equipment can be prepared by many other methods.As, a polyester film adhesive tape and a metallo-plastic adhesive tape are coupled together, wherein on polyester film adhesive tape, there is a PSA (adding an orchil/pigment) containing activator.Described biobelt can be glued together, heat seal, ultrasonic soldering etc.Also have a kind of method be plastic sheeting that can hot print use a kind of PSA (adding an orchil/pigment) containing activator below, then splice a metallo-plastic film.Many miscellaneous equipments of the present invention also can be prepared from by these and other method of the present invention.

Method 3: get a metallo-plastic film, hot print coating (being generally thermal printing paper and coating) is coated in to its plastic side.Described film can be by warm, ink-jet, the printings such as laser.An image can be shown as black and white according to the character of contained micro-capsule and material, coloured, or transparent.Use a kind of activator to bring the described equipment of activation in metal side.After metal level is corroded, it can change the outward appearance of image.

IIMAK (the transparent D.T. of production code member #TF200C, Amherst, New York) visitor card (1) of sending out of core printed a photo on a hot print film, it has formed a psa layer containing the activator composition described in embodiment 3 after hot print, and (2) are pressed onto active agent layer on a metal-polyester film.After metal level is corroded, photo can become transparent.

Vice versa, and micro-capsule is protection indicator or protection help of indicator particles.

Activator band and indicator strip can separate, and can be also interconnective (as bonding/splicings), and their size and shape can be identical or different.Described equipment can be by a belt is applied on another belt, or the belt being folded to connect activates.

Coating on base plate can only contain indicator (as clad metal powder), only contain activator (as the phosphoric acid of encapsulation), a kind of encapsulation and another do not have (for example encapsulate phosphoric acid, but not coated metal powder) or hybrid package indicator and activator.This coating can contain other adjuvant.According to the difference of application, base plate can be transparent, opaque, coloured, by what apply wholly or in part.Base plate can carry out extra coating as required.Coating can have one or more protective finish.The thickness of coating also can be arranged to 1 micron to 1000 microns not etc. according to application.

In described coating, there is a kind of dyestuff or indicator that changes color.

Described coating can be made up of two or more encapsulating material and a kind of acid, wherein encapsulating material can be used as a kind of indicator as a kind of leuco dye or pH sensitive dye (front look/change look), and it is sour, as phosphoric acid can be used as a kind of activator, and only optionally discharge activator.This coating also can be made up of metallic particles (packed/to apply or do not have) and the activator of encapsulation.Various combinations are all fine.

Physics and chemistry method, as it is dry to spray, and sprays cooling, rotating disc atomization, fluidized bed coating, fixed nozzle co-extrusion, spinning head co-extrusion, mouth of a river co-extrusion, pot coating, be separated, solvent evaporation, solvent extraction, interfacial polymerization, simple and complicated co-activating, in-situ polymerization, liposome technology and nanometer encapsulation all can be used for encapsulating indicator of the present invention and activator.Body of wall or sheathing material, as protein, polysaccharide, starch, wax, fat and lipid, natural and synthetic polymer and resin all can be used for encapsulating indicator of the present invention and activator.

The chemicals of many encapsulation, as sodium bicarbonate, sodium bromide, sodium chloride and sodium Diacetate are all commercial.They can be used as the activator of equipment of the present invention, are preferred for the indicating equipment of sterilizing.Other also can encapsulate similarly and use

United States Patent (USP) 4675161 discloses epoxy coating microcapsules and azo dyes for sterilization, comprises the sterilization of heating and oxirane.But the not open use to other dyestuff and other materials for wall.

We find, the hot coating that some dyestuff directly makes is too responsive to EO gas.Can be coated in a metal PET and be coated with thinly a metal (as 10 dusts) or the reaction of lamination metallo-plastic film as described in slowing down thinly, the sheerly metal at film has optionally quick/interval.Utilize wedge metal film can form mobile border EO equipment.

We find, commercial direct heat Print Label (for example, the mine-laying enlightening that those are available, IIMAK and Federal Express and UPS use) while at room temperature contacting with moist or dry oxirane (EO) gas, understand and in minutes become gradually black.Label same but that scribble Joncryl 77 (Johnson andSons, Racing, WI) can become black more lentamente.Therefore, select suitable materials for wall, barrier coat and/or dyestuff, can make coating after EO gas depoisoning, become the required time of black various.

Because these labels are normally stable in environment, therefore they can be for monitoring EO gas.

These labels also can be in the hydrogen peroxide vapor of 50 DEG C a whole night.They also can deepen a little.But the old dot matrix facsimile transmission paper that we buy Liao Kuier company in the later stage eighties becomes black in several hours unexpectedly at 50 DEG C.It seems, materials for wall and/or protective finish more easily penetrate hydrogen oxide.The dyestuff using due to heat or dot matrix paper is reducing dye, and they also should be at other oxygenant, as become black/coloured in Peracetic acid and ozone.

Indicating equipment of the present invention is that naked eyes are readable, and it also can read more accurately with machine.Our being entitled as general high precision dosage read the equipment described in the U.S. Patent application #20080023647 of instrument and method also can be used in the present invention.Equipment described in U.S. Patent application #20080023647 and pertinent literature and method can be used as reference of the present invention.

Compositions more of the present invention, equipment and process, for example, and gummed tape, two information, if " effectively " is to engineering noise, " fresh " arrives " stale ", and " not sterilization " all can be used for the composition of prior art to " sterilization ", in equipment and process.For prove invention can be suitable for widely, we have made various existing equipment, as the time, Time-temperature, radiation, freezing, thaw, microwave boils, hot water wash the dishes indicator and sterilization indicating equipment, make it to there is the present invention.Some representational examples are summarized as follows:

We use a kind of activator band and label of phosphoric acid on a commercial hot print band, thus a strap of preparation.On the box of a sealing with the word of " fresh ".Box is to seal with a hot print film/band (iimak, the transparent D.T. of production code member #TF200C, Amherst, New York) with the transparent/translucent of pressure-sensitive adhesive.In hot print coating, used a kind of pressure sensitive adhesive activator band, it contains phosphoric acid (being embodiment 5).Box is placed at 60 DEG C.Colourless coating in 1 hour, gradually become light gray green-> celadon-> grey-> black.Similarly box is at room temperature placed change color is just occurred for one week.

" fresh " printed with thermal printer in clear, thin film labels (being provided by IIMAK) top at hot print.In the bottom of film, with band latex, " stale " of Joncryl 74, makes it dry." stale " mays be seen indistinctly.Use an activator band in embodiment 5.Described equipment is placed in the baking box of 60 DEG C.Word " fresh " region is around dimmed gradually, and word " fresh " is substantially not obvious.Meanwhile, word " stale " is dimmed, makes it more obvious.In hot print coating, use an applicable pervious course, can make significantly " stale " to match with unconspicuous " fresh ".These equipment can be used as TTI monitors shelf-life of perishables.The miscellaneous equipment of " effectively " and engineering noise has equally this word, as also can demonstrate,proved for the preparation of visitor.

We are coated in hot print coating by the wedge shape pervious course that a polyvinyl acetate emulsion is made, and use a kind of activator of phosphoric acid, have also created a moving boundary equipment.Equally, many other equipment of the present invention, for example barcode device, bandage indicator, sterilization indicator, hot water indicator, micro-wave oven boils indicator, utilizes the indicator that thaws of phase detachment technique, humidity indicator, amendment indicator, radiation indicator and novelty can use existing composition, equipment and process and of the present invention preparation.Although we have used phosphoric acid to prove some concepts as activator and hot print film, also can use other indicator and activator.Some suitable variations may be essential.

The equipment of prior art, particularly variable color equipment can be made and automatically read.For example, if sensing material is acetylene UV light exposure (using ultraviolet laser) sensor so, if sensing material be heat sensitive be so thermal pretreatment or be only printed on a suitable marking.Can produce code, bar code, information etc.Acetylene is very sensitive to ultraviolet ray and thermal annealing (i.e. time and the temperature of storage), therefore can auto-activation.The described equipment of activation as required.After regular hour and/or Time-temperature, the expired information of the change color of sensor and the instruction of printing matches.

In all existing equipments, change color is gradually.

Equipment of the present invention also can use the automatic expired ID of ID or Gao Min, and they are with or without RFID.Also can according to concept of the present invention with become to assign to prepare various expired products automatically.

Described equipment also can be produced on production line.For example, (1) print an indicator strip (as metallo-plastic film) containing activator, vice versa, on (2) activator, has indicator, vice versa, or (3) spray simultaneously or ink sprays activator and indicator simultaneously.

Can develop and use the software of monitoring registration equipment of the present invention.

Because a kind of activator and a kind of metal react, therefore different indicator and activator can produce different accessory substances.If needed, can utilize analysis accessory substance and concentration thereof further to analyze described technique, degree for the treatment of and described equipment.

Various creation of the present invention (composition, equipment and process) can be simply for the miscellaneous equipment in various sources.

Design of the present invention can be replaced.The design of an indicating equipment can or be carried out suitable change for other required indicating equipments.The for example information of " expired " and red time-temperature indicating equipment can replace with respectively " sterilization " and green sterilization indicating equipment.

Various process/equipment can be developed for binders for coatings, ink, paint and other polymeric material.Common coating process has: air knife, hairbrush, film-discharging machine, casting coating, curtain, inclination angle, extruding, blade, floating cutter, intaglio printing, kiss roll, offset plate, reverse rollers, bar, spraying and compression roller.Above-mentioned most methods all can be used for matrix to be coated on various basic materials.

Can adopt various printing processes to print suitably activator and indicator, thereby prepare various indicating equipments.Ink can contain a kind of activator or metal indicator.For example shape is that the indicator of an information is printed in an active agent layer, and vice versa.Substantially any ink or typography, comprise ink-jet, laser tonne, and dye sublimation and traditional ink and technique can be used.

Water and molten molecule ink-jet ink are commercially available.The mark of message form can be printed on an ink-jet ink simply, and without any need for pigment or contain described indicator, preferably activator.Ink can be also uV curable.

Serigraphy is also for the manufacture of sterilization indicating equipment.Also can prepare plastic cement colloidal sol, water and molten molecule, realize serigraphy and prepare indicating equipment.These indicator, activator and precursor dispersible or are dissolved in a kind of plastic cement colloidal sol or very in the carrier of thickness, as Polyvinylchloride plasticized polymer and similar polymkeric substance.

Many chemicals can be monitored with change color reagent, and the variation of color can occur in the time that it reacts with chemicals.Be filled with a kind of inert substrate, and the clear glass and the plastic tube that scribble these change color (detect/instruction) reagent are widely used in monitoring various hazardous chemicals.The air of getting dirty of known volume passes a described pipe that is filled with these reagent, and monitors its change color.

Metal and alloy thereof also can react with many chemicals, and these chemicals are used as activator and activator precursor in the present invention.Inert material, porous or atresia, the shallow layer of metal and common alloy also can be for monitoring a large amount of chemicals.Inert material can be opaque, can be also transparent, for example, and glass or plastic bead, sheet, fiber, film and sheet.An empty glass test tube inner thin unfertile land scribbles a kind of suitable metal or its alloy, or solid fiber scribbles a kind of suitable metal thinly or its alloy also can be for monitoring some chemicals.

Various difform metal base plates can be for monitoring chemicals.They comprise metallized optical fibre, pipe, sheet, band, pearl.

Except monitoring activator of the present invention and activator precursor, above-mentioned metal base plate also can for detection of/monitoring carboxylic acid and chloric acid, as formic acid, acetic acid, acetyl chloride, ammonia and amine, for example methyl amine, ethamine, diethylamine, pyridine and aniline, halogen and halogenide, as chlorine, chlorine dioxide, mineral acid, example hydrochloric acid, hydrofluorite and nitric acid, sulfide, as mercaptan and methyl mercaptan, sulfuretted hydrogen and carbon disulphide, oxide, as sulphuric dioxide, nitrogen dioxide, phosphine and oxychlorination carbon, the cresols such as phenols, oxygenant is as hydrogen peroxide etc., also comprise ozone, hydrocyanide, as formaldehyde, furfural, epoxide, as oxirane, epoxypropane aldehyde, superoxide, and epichlorokydrin, metal, as mercury vapour, oxygen, carbon dioxide, carbon monoxide, its reaction such as water/humidity and chemicals can be by metal and metal alloy catalysis.By selecting suitable metal and alloy thereof, also can optionally realize some chemicals.

This reaction is visual thereupon, or by monitoring electric conductivity, comprises the variation of ionic conductivity.After metal is corroded, its electric conductivity can decline.

Biomaterial and organism, alive or dead, bacterium, virus, steel strand wires, enzyme, protein etc. can generate a kind of metal level activator, and therefore metal level can be used for monitoring bio material.Biomaterial may need a so-called base plate, and a kind of reactant in the product that a kind of biomaterial generates, is now a kind of activator or a kind of catalyzer.This biomaterial can be used for analyzing the material of human body, comprises urine and blood.Body part and fluid have a large amount of inorganic and organic chemicals (biological chemistry) works), as acid, salt, sugar, nitrite, amino acid and enzyme.By selecting suitable substrate, enzyme, media, precursor, catalyzer etc., just can control the reactant character that generates a kind of activator, and described activator can react with a thin metal layer, corrodes this thin metal layer.Product can corrode some metal and/or alloy as G-6-P.

Because metal and oxide thereof and complex can react with many chemicals, therefore their (particularly shallow layers) can be used for measuring its concentration.For example, aluminium and much acid, alkali and reactant salt.A thin metal layer that dissolves known thickness, the time as required in the fine aluminium of 100 dusts is by specific acid, the concentration of alkali or salt determines.Once calibrate, scribble the base plate of a thin metal layer, this base plate can have a permeation coating, also can not have, and it can be used for monitoring various chemicals, comprises the concentration of toxic reagent.

We find also to use a thin metal layer, as the metallo-plastic film or do not have with precursor layer is monitored a large amount of chemicals/reagent.The much poisonous chemical mass-energy such as bromine with react as metals such as aluminium.

Material of the present invention, the war chemicals that equipment and method can be monitored comprises fatal, oedema, blood, nerve, lung, anergy and anti-riot controlling agent.These examples comprise hydrogen cyanide and cyanogen chloride, ethyl dichloroarsine, methyl dichloroarsine, phenyldichloroarsine, lewisite, 1, the chloro-3-ethyl thioether of 5-bis-, 1, two (the 2-chloroethyl sulfenyl) ethane of 2-, 1, two (the 2-chloroethyl sulfenyl) n-propanes of 3-, 1, two (the 2-chloroethyl sulfenyl) normal butanes of 4-, 1, two (the 2-chloroethyl sulfenyl) n-pentanes of 5-, 2-chloroethyl chloromethyl thioether, two (2-chloroethyl) thioether, two (2-chloroethyl sulfenyl) methane, two (2-chloroethyl sulfidomethyl) ether, two (2-chloroethyl sulfidomethyl) ether, two (2-chloroethyl) ethamine, two (2-chloroethyl) methylamine, three (2-chloroethyl) amine, tabun, sarin, rib is graceful, cyclosarin, GV, VE, VG, VM, VR, VX chlorine, chloropicrin, phosgene, azobenzene, (BZ) 15 doses, 3167 doses of EA, nauseant, capsicum water spray, CS gas, CN gas or CR gas.

Material of the present invention, the poisonous industrial chemical that equipment and method can be monitored comprises acetone cyanohydrin, acryl aldehyde, vinyl cyanide, vinylcarbinol, allylamine, allyl chlorocarbonate, allyl group isosulfocyanate, ammonia, arsenic trichloride, arsine, Boron tribromide, boron chloride, boron trifluoride, bromine, bromine chloride, BPF, bromine trifluoride, carbon disulphide, carbon monoxide, carbonyl fluoride, cos, chlorine, chlorine pentafluoride, chlorine trifluoride, chloroacetaldehyde, chloro-acetone, chloroacetonitrile, chloracetyl chloride, chlorosulfonic acid, crotonaldehyde, cyanogen, 1, 2-dimethylhydrazine, diborane, ketene dimer, dimethyl suflfate, diphenyl-methane-4, 4 '-diisocyanate, ethyl chloroformate, thio-ethyl chloride, ethyl dichloride EPN, ethyl phosphorus dichloride, dibromoethane, ethyl imines, oxirane, fluorine, formaldehyde, hexachlorocyclopentadiene, hydrogen bromide, hydrogen chloride, hydrogen cyanide, hydrogen fluoride, hydrogen iodide, hydrogen selenide, sulfuretted hydrogen, iron pentacarbonyl, isobutyl chlorocarbonate, isopropyl chloride, isopropyl isocyanate, methylsufonyl chloride, methyl bromide, methyl chloride, methyl chlorosilane, methyl hydrazine, methyl isocyanate, methyl mercaptan, butyl ester chlorine, n-butyl isocyanate, nitric acid, flue gas, nitrogen monoxide, nitrogen dioxide, normal propyl chloride, parathion, cross chloromethyl mercaptan, phosgene, hydrogen phosphide, phosphorous oxychloride, phosphorus pentafluoride, phosphorus trichloride, sec-butyl chloride, seienium hexafluoride, silicon tetrafluoride, antimonous hydride, sulphuric dioxide, sulfuric anhydride, sulfuric acid, chlorosulfuric acid, vikane, tellurium hexafluoride, tert-butyl group isocyanates, tert octyl mercaptan, lead tetraethyl, tetraethyl pyrophosphoric acid, tetramethyl lead, titanium tetrachloride, toluene 2, 4-diisocyanate, toluene 2, 6 diisocyanate, trichloro-acetic chloride, trifluoro-acetyl chloride or tungsten hexafluoride.

Equipment of the present invention uses a metal or metallic particles layer as a kind of indicator and activator or chemical layer, activator or chemicals can with the metal destruction metal that reacts.Result just can be measured the conductivity of conductivity, especially present device, conductance, and resistance and resistivity are monitored the process of reaction/phenomenon.It is salt solution substantially that conductivity can become from about every meter of 37 × 106 Siemenss (S.rrf1), i.e. about 5S.rrf1 or lower, if aluminium is as a kind of indicator.This is to exceed the variation of 1,000,000 times in conductivity.Therefore, many phenomenons of the present invention can be monitored accurately.Use the method for this measurement conductivity can measure ppm (1,000,000/) concentration and ppb (the 1000000000/) concentration of chemicals.Measure many other characteristics of Conductivity Ratio measurement simpler.

Metallic film or the fiber that scribbles metal level can apply an a kind of activator, precursor, and catalyzer, biological base plate is optionally monitored more than one chemicals or a kind of reagent that contains chemicals or biological reagent.

The length that increases conductive path can further improve precision.For some equipment, can be by folding or realize with metal fibre.Several method all can be used for making equipment to fold or spiral conductive path.For example, for making the method for printed circuit board (PCB), fire a metal surface or a kind of make improving one's methods of CD (CD) with laser.

Some equipment does not need superhigh precision, as the time, and temperature, defrosting, freezing, microwave sterilization indicating equipment.Centesimal more high precision is that some equipment is preferred, as the time showing equipment in the moon or year.But some equipment need very high precision, as the monitoring of radiation estimator and chemicals.If can reach than one percentage point more the high precision of fraction come measuring radiation and chemicals, so just can monitor accurately low dosage.According to the linear conductivity of expection, can in a very wide dosage range, realize high-precision dosage measurement.

By conducting particles, a kind of electrically-conducting paint of activator and bonding agent composition can be used for preparing much equipment of the present invention, and the phenomenon causing for monitoring conductivity variations.

Instant fiber waveguide device and the prior art of invention are basic identical, except described instruction/molten coating will be metal or alloy, and have or do not have outside an activator or its precursor layer.Described optical fiber can be metallized by the method described in document, as United States Patent (USP) 6,798, and 963 and 7,158,708.

Detecting devices can be developed the variation for surveying chemistry or physical parameter, comprises sensor fibre, and the core core that it has a metal or alloy thin layer to comprise is with or without an activator or its precursor layer.

This equipment can have one and not establish metal and/or activator coating or associated fiber not processed or that expose.

The core core of this sensor fibre can be basic identical with the core core of optical fiber.

This equipment can also be made up of two optical fiber, and the first extends to respectively a light source and detector by every one end of the sensing fiber being connected with its far-end.In addition, single optical fiber can start to extend from sensor fibre, and the other end is made reflective, and the individual transmission optical fiber being all connected with detector with light source can use a spectroscope.

Due to the uneven enlargement and contraction of cladding material (metal) and core core material (glass or plastic optical fiber), therefore can use the many physical phenomenons of monitoring of equipment of the present invention, as temperature, pressure and pressure.

In order to monitor physical phenomenon, as the time, temperature, freezing, thaw, Time-temperature, radiation etc., need an active agent layer conventionally, and this active agent layer is arranged on metal level, or vice versa.But for the equipment of sterilization and monitoring chemicals, activator must be coated on whole metallic coating.

Conductor layer can be also semiconductor layer.

On activator being coated in to a metal optical fiber, also similar equipment can being put into a kind of solution or liquid activating agent or activator precursor and prepare.This equipment can be faster, more responsive.

Base plate in these equipment can be the optical fiber that a kind of glass or polymkeric substance are made.

Optical waveguide of the present invention is conducted electricity, and therefore also can monitor all these phenomenons by the variation of monitoring conductivity.

Activator of the present invention and activator precursor can be for light guides.Described activator and precursor thereof can dissolve or spread in the polymer-bonded thing of one, and are coated in the metallization after an optics of metals fiber or coating.They also can be applied by some traditional paint-on techniques, as dipping, vacuum evaporation/distillation.

These optical waveguide indicating equipments also can have the feature of time of the present invention and Time-temperature indicating equipment.

Similar to conductive equipment, described light guides also can be more accurate.

The quantitative variation of the reacting phenomenon of equipment of the present invention also can be measured by other parameter, as the variation of magnetic and reflectivity, and the variation that transmission and spectrum move.

All indicating equipments and part thereof also can be made roll forming.So indicating equipment roller may be cut open or remove the peel, and uses on object.The shape of this indicating equipment can be, for example, circle, ellipse, other shaped form, preferably symmetrical, triangle, square, rectangle, sexangle, and other polygon, comprise regular polygon and equilateral polygon.

All indicating equipments of the present invention can be various types of indicating equipments, and as a kind of temperature indicating equipment of TTI, the ammonia indicating equipment of TTI, has the sterilization indicating equipment of Time-temperature or temperature indicating equipment or the radiation indicating equipment of TTI.

Can on an object or base plate, monitor two kinds of different conditions with more than one indicating equipment, therefore a kind of equipment will send the information of a setting, and another sends the information of other type or is sending thereafter.

Equipment of the present invention can combine preparation multi-process and many materials indicator.For example, a TTI on radiation indicating equipment, or vice versa, and can be for the perviousness of monitoring radiation, as food and blood and shelf-life.Indicating equipment also can have other indicating equipment, as temperature indicating equipment.

In different processes, can process different processes with one or more activators, for example, a kind of activator for steam and oxirane, or a kind of activator for steam and the another kind of activating mixtures for oxirane.Described equipment also can be for two or more processes, as steam, and oxirane and plasma.Can be by selecting more than one activating mixtures, preferably the potpourri of independent activator is processed each process of its expectation.

Following one or more major parameters can change the activator energy of required time of transparency change and indicating equipment of the present invention: the 1) thickness of activator matrix, 2) indicator and the altogether thickness of indicator, 3) thickness of pervious course, comprise an oxide layer, 4) concentration of activator and coactivator, 5) concentration of precursor, 6) concentration of adjuvant, 7) solvent, the character of surfactant and catalyzer, 8) character of activator matrix, 9) indicator and the altogether character of indicator, 10) pervious course, comprise the character of an oxide layer, 11) character of activator and coactivator, with 12) a kind of character of adjuvant.All parameters can change the required time of transparency change.Parameter 1-6 only can change the required time of transparency change, and parameter 7-14 can change activator energy and required time of transparency change.

These equipment and relevant technique are used metal as a kind of indicator, use mordant as a kind of activator, and they provide more following main specific characteristics, and this does not have in other indicating equipment:

Indicator:

The thickness ultrathin of indicator layer, only has～100 dusts.

Indicator is a kind of nontoxic metal, normally aluminium, and the salt of this metal is also nontoxic.

Metallo-plastic film is different-thickness (～25 dust-700 dust), the aluminium lamination of different colours.Therefore do not need to prepare indicator strip.

The aluminium lamination that 100 dusts are thick provides 99% opacity.Approximately 20 dusts are translucent, but reflecting rate and opacity are lower than 10 dusts.

Mean accuracy is about 80%, but is also possible up to 99%.

From opaque, reflective become transparent.Reflecting surface is easy to be noted.

Metal ink can use simply.Commercial aluminium (i.e. silver) and a kind of bronze (a kind of ormolu, i.e. so-called gold) ink can be for replacing metallo-plastic film.

Some metals and a large amount of alloy thereof are inconsistent to the susceptibility of different activators, but they may be used to prepare various indicator, and use and have material of different nature in various technique.

Indicator can not volatilize or fade.

Reaction can be carried out in conventional non-toxic material, as water, and oxide, acid, alkali and salt.

A large amount of activators and activator precursor can be for improvement of various indicating equipments.

Apply one deck and prepare activator band containing the pressure sensitive adhesive (PSA) of activator.PSA is the technology that a kind of quilt better develops with technology.

Reaction:

Reaction is 100% irreversible.

This reaction is various.It only can occur in metal surface, therefore produces zero order kinetics, and temporal evolution is linear, and this is one of optimal characteristic.This also makes this equipment very accurate.The reaction that nearly all indicating equipment occurs is all the first rank/asymptotic conventionally, starts fast, then slowly slack-off.

Reaction product is normally colourless, the salt (using metal, as aluminum and zinc) of white.

Marker is ultra-thin, or even opaque reaction product, as aluminium oxide approaches transparent substantially.

Even if reaction has stable incidence, opaque layer only becomes transparent in the time of remaining 10-20 dust unreacted.Therefore, it can produce a very long induction period, and it can be most preferably for removing/do not go the indicating equipment of type.

Color and information

Conventionally can there is a change color in a kind of indicating equipment.Can there is transparency change in these equipment.

Transparency change makes it can under metal level, print any information or color, as nonrestrictive whole color/information is provided.

A part of information (as " good ") is imprinted on whole metal level, another part is imprinted under metal level (as " non-); just can form two information (good-> is bad; fresh-> is stale, not sterilization-> sterilization).

Also mobile boundary line equipment be can form and a process or material monitored continuously.

This can read equipment automatically, accurate and foolproof proof.

Mechanical-readable and remotely readable.

Application:

Use suitable right activator and indicator, can monitor various materials and technique, comprising:

-the time (as automatically expired visitor's card, using ID)

-temperature (as microwave boils)

-time-temperature (as the shelf-life of monitoring perishables)

-freeze (as fresh blood, goods, some vaccines)

-(as frozen food) thaws/defrosts.

-humidity (as medicine and food).

-sterilization (as the sterilization of monitoring medical supplies and perishables):

Steam

Oxirane.

Plasma/hydrogen peroxide

Radiation.

-nonpoisonous chemicla and biomaterial (as chemicals and biological reagent)

-electronic equipment

RFID

Electronics monitoring

Circuit board

Indicating equipment/the monitoring technology being necessary and do not have is available, wherein:

Automatically read and foolproof proof.

Unlimited color and information is provided.

Be provided long induction period, and it has and does not go two information.

For some materials and technique, as universal technology provides identical color.

Precision is high, mechanical-readable and remotely readable.

Very economical.

Be suitable for independent element, be also suitable for the set of element.

Equipment of the present invention has these and many other required characteristics, has filled up technological gap.The combination of all these and many other desirable characteristics makes equipment uniqueness.They are true required indicating equipments.

The large number quipments that some manufacturers provide, as the time, temperature, Time-temperature, freezing, thaw, sterilization and radiation indicating equipment can be commercial.Be used in a specific indicating equipment, as moise-heat sterilization indicating equipment, there be oneself color, change color, size, shape and the design that is different from others in each manufacturer.Therefore it need to be trained user and how to use and to understand.Automatically the equipment reading of the present invention does not need user to give training, and all indicating equipments are all basic identical.Therefore this technology provides a chance to popularize described indicator technologies.

example

The indicative explaination of the realization of example below to the claims in the present invention, but should not be understood to be the restriction to scope of the present invention and meaning.

Example 1: prior art

The AVERY DENNISON's of California Pasadena Double-magnetic tape TTI equipment, activates by being applied in the activator band (containing PSA acid on clean plastic foil) that (contains resin PH coloring agent on white plastic film) on indicator strip.At room temperature one day and in 50 DEG C of next ones hour, activation equipment was generally from the variation of Huang-> lilac-> purple-> darkviolet.Differentiation/the variation of color is rapid and slow in the time of knot speed in the time starting.Because being based on there, the diffusion of equipment there is no unexpected change color.

Example 2: the impact of phosphoric acid and concentration thereof.

Prove the feasibility of this concept with the metallized polyester films of one 100 microns (thering is the aluminium lamination of 125 dust thickness).

On the metal level of metallized film, write letter " A " and be placed on after a film on red paper and write " 1 ", then to the phosphoric acid of toppling over 1mL 85% on " A ".After approximately 4 minutes, on aluminium lamination, there is a small amount of bubble (hydrogen).Red paper and " 1 " 5 minutes are all invisible.Aluminium lamination dissolves completely with red paper and becomes completely as seen after 6 minutes.Therefore, this equipment has makes change color (silver color is to red) very long induction period (about system 80%), that is, within 5 minutes, be there is no red probably occurring in one minute with redness.Have shown in example 33 and Figure 44, completely dissolution of metals layer need time be increased to 15% phosphoric acid for 6 minutes 38 minutes from the phosphoric acid with 85%.

Example 3: for the preparation of the bonding molecule of activator of activator band.

In 500 ml beakers, add 150gPSA (production code member S8510, AVERY DENNISON, Pasadena, California), the phosphoric acid of 150g isopropyl alcohol and 25g 85% also mixes.The concentration of phosphoric acid need to be different according to equipment.

Example 4:PSA molecule, concentration and activator solvent are on the etched impact of metallized polyester film.

A mylar of 100 microns (here referred to as 100 micron metal polyester film or metallized polyester film) with the aluminum coating of approximately 125 dust thickness is placed on a red paper, then in the metal edges on film right side, topples over PSA molecule 1 mL as described in Example 3.All sightless at nearly 25 minutes red paper.Aluminium lamination dissolves completely with red paper and becomes completely as seen after 35 minutes.The needed time of dissolution of metals layer is relevant with several factors, as concentration, and solvent, temperature, aridity and the thickness of dry active agent layer.

Example 5: the preparation of activator band.

Brush the activator described in example 3 is coated on the polyester film of 100 microns clean (non-metallic) with #50 and #30 metal lean.Coating is dry 10-15 minute at 70 DEG C.Some activation film that has covered 50 microns of polyester release films that scribble resin silicon on both sides at another side is used for making apparatus, will carry out Preparation equipment with the diaphragm that these are being removed after release film at more ensuing examples.

Example 6: the preparation of simple device

Have on one side the metallized polyester film of a red coating bonding the activator band that there is psa layer and come covering metal layer described in an example 5.Activator has dissolved that on the metal level of equipment, then red color is visible, after at ambient temperature 5 hours and under 60 DEG C of conditions after 30 minutes.When equipment is annealed under 60 DEG C of conditions, there is some bubble phenomenon or metal level cracking.

Activator strap described in example 5 is applied in seven and covers the 50 micron metal mylars (obtaining CP film from processing industry garden, Kano, California) on metal level with different colours coating with PSA film.CP film forms by three layers.50 microns of mylars have the color ink that one deck is very thin and are coated on the aluminum coating with 125 dust thickness.Bonding film is placed in the drying box of 55 DEG C.Metal level is dissolved in about one hour completely and ink colors becomes visible.

Equally, adopt and metallize on the both sides of mylar and coat activator on the both sides of mylar and carry out making apparatus.

Control Example: activator strap is applied on the aluminium foil of 15 micron thickness and anneals several weeks at 50 DEG C.This band does not dissolve this paillon foil.But when placing several phosphoric acid on the aluminium foil of 15 micron thickness same, this paillon foil dissolves completely in 1 hour at 50 DEG C.

Example 7: the preparation of the equipment of certainly reading of similar Fig. 7.

7.1 have the activator band of a part of information: on the clean mylar of 100 micron thick, print vocabulary " fresh " with laser printer.The back side at this film is brushed and is had the activator of one deck example 3 and be dried 10 minutes at 70 DEG C with #30 metal lean.

7.2 have the indicator strip of another part information: upset/mirror image and the bar code of on the non-metal surfaces of 100 micron thick metallized polyester films, printing vocabulary " character is unsecured " with laser printer.

The activator of 7.3 equipment: activator band is applied on indicator strip, has bonding agent (activator) layer and covers metal (indicator) layer.The applicable arrangement of touching is focus.Equipment obtains and refrigerated storage from thin plate/active membrane [seeing Figure 33 (a)] cutting.

7.4 testing of equipments: some equipment are (25 DEG C, 45 DEG C and 55 DEG C) at different temperature.These equipment are taken out and are carefully checked at different time interval from drying box.At the visible vocabulary in the top of equipment " fresh ".Equipment shown in Figure 33 is at 25 DEG C, to anneal 27,34 and 38 hours.25 hours information " character is unsecured " and bar code at 25 DEG C, are crossed invisible.As shown in Figure 33 (b), they start to appear at after about 27 hours, as shown in Figure 33 (c) they almost after about 34 hours and as shown in Figure 33 (d), they are completely readable after about 38 hours as seen.This equipment has about 70-80% induction period.Can extend by a permeable layer.This equipment is from reading.

The energy of activation of reaction is by determining the logarithm icon of 1/T (T=absolute temperature) induction period.The energy of activation of equipment is approximately 7 kcal/mol.The monitoring time of equipment prepared by low-activation energy is more satisfactory, as guest id card.

Having the equipment that different types of information (comprising different symbols and language) comprises that minority has two bar codes all can manufacture.

Example 8: there is the preparation of the equipment in the removable boundary line of wedge shape permeable layer.

8.1 activation zone.On 100 microns of clean polyester films, brush with #30 metal lean the activator that has described in example 3 and at 70 DEG C dry 10 minutes.

8.2 have the indicator strip of wedge shape coating: the Hydrin that is used in 10% concentration in toluene scribbles the piece of 0-250 micron wedge shape 10 centimeter length and be dried 5 minutes at 70 DEG C on the metal surface of 100 micron metal mylars.The wedge shape coating of Hydrin obtains has the 0 wedge shape coating to about 25 microns of dry thickness.

Some films scribble the wedge of 0-250 micron 5 centimeter length.

Some metallized polyester films are printed with grade red and numeral and black and grey on uncoated.

The activator of 8.3 equipment: activator band is applied on indicator strip, has bonding agent (activator) layer and covers metal (indicator) layer.A lot of equipment is to cut into wide about 1-2 centimetre.

The test of 8.4 equipment: some equipment are (25 DEG C, 45 DEG C and 55 DEG C) at different temperature.These equipment are taken out and are carefully checked within the different time cycles from drying box.Shown in Figure 34, be the equipment of annealing under the different time cycle at 55 DEG C.As can be seen from Figure 34, create boundary line by dissolution of metals layer and boundary line moves to thick end from the thin end of the wedge shape coating of Hydrin with annealing time.The movement in boundary line is almost linear with the time.

In mobile boundary line equipment, aluminium lamination attenuation can be seen (as the transparency of metal level increases clearly gradually), and this shows to react on surface.

Boundary line moves substantially linear with the time, i.e. zero-order reaction, and most of indicators are a uniqueness and most suitable characteristic.The linearity that boundary line moves is produced by the combination of many parameters but is mainly due to two reactions, and (1) activator is in the expansion phase of permeable layer and the etching of (2) aluminium lamination.Change color/the differentiation of all known time and Time-temperature indicating equipment are all progressive (being first order reaction).Color develops in the time starting and becomes rapidly and in time slow.

The characteristic that current equipment can be thirsted for is very much exactly that indicating equipment has in time and the very long induction period of linear change color.

From Figure 34, clearly can find out, can increase induction period by the thickness that increases pervious course, the thickness of layer is just longer larger induction period thoroughly.

The dynamics of 8.5 diffusion/reaction.

The displacement in boundary line is determined by the annealing of (25 DEG C, 45 DEG C and 55 DEG C) at the different temperature of equipment.Energy of activation is determined as the logarithm icon of 1 and 2 centimetre of 1/T from the logarithm of the displacement that requires of time.Energy of activation is 21 kcal/mol.Energy of activation is higher, may be the reaction due to diffusion, i.e. the pervious course that has diffused through Hydrin of phosphoric acid.

Example 9: the pervious course of different-thickness

9.1 activator bands.On 100 microns of clean polyester films, brush with #30 metal lean the activator that has described in example 3 and at 70 DEG C dry 10 minutes.

9.2 have the pervious course of the indicator strip of different-thickness: on the metal surface of 100 micron metal mylars, scribble one 27,75 with the Hydrin of 10% concentration, the piece of 125 and 300 microns also at 70 DEG C dry 10 minutes.

The activator of 9.3 equipment: activator band is applied on indicator strip, has bonding agent (activator) layer and covers metal (indicator) layer.A lot of equipment be cut into and annealing at 45 DEG C.Aluminium lamination dissolves record of needed time completely.Shown in table 1, approximate pervious course thickness and aluminium lamination dissolve the needed time

Table 1 is similar to pervious course thickness and dissolves the needed time at 45 DEG C of lower aluminum layers.

Thickness (mil)	Dissolution time (hour)
		0	3
0.015	5.5
		0.03	13
0.05	23
		0.06	28

Therefore, metal level dissolves the needed time and can change by the variation in thickness of pervious course.

Example 10: strap

The one side of 50 microns of clean mylars is printed with red background " expired, can not sell, return to manufacturer " and another side and scribbles the activator band that the activator described in example 3 is made.This activator band becomes active equipment with indicator strip (metallization PET film) bonding (activator/adhesive phase covers metal/marker).Be cut into approximately 5 centimetres wide rectangular.These rectangular being placed on 5 centimetres of wide bands available on market.(5 " x 5 " x 3 ") close and use the active belt as shown in Figure 35 (a) to seal and store at room temperature little box.At room temperature information start occur greatly after 18 hours and as shown in Figure 35 (b) completely as seen after 25 hours.

Can after active equipment, be applied to another to picture with PSA.

The indicating sealing carrying device of other several types is also manufactured, as, (1) by adopting wedge shape pervious course and bringing the wedge-type seal carrying device that has wedge shape psa layer and manufacture mobile boundary line of activation by activity, (2) have vocabulary " fresh " and have " no " at back with narrow metallized polyester band and (3) under activator band at top.

Example 11: the guest id card with removable boundary line.

With laser printer 100 micron metal mylars do not have on metal covering, print a sheet photo.The Hydrin that is used in 10% concentration in toluene on the metal covering at the photograph back side is coated with the wedge of last layer 0-250 micron and is dried, and the back side of 100 microns of opaque mylars scribbles activator the dry activation zone of making described in one deck example 3.Make equipment (guest id card) there is activity by the activator in application wedge shape coating.Consequently, the tag card as shown in Figure 36 (b) is placed in the drying box of 55 DEG C.As shown in Figure 36 (b)-36 (f), after 2 hours, occur in the bottom of photograph that black boundary line and boundary line are along with the time moves up.At room temperature spend the time of nearly one month that boundary line is moved at the other end from one end.

Example 12: the guest id card with red background and X.

With laser printer 100 micron metal mylars do not have on metal covering, print a sheet photo.On red mylar, print the X of black and scribble activator the dry activation zone of making described in example 3.Make equipment (guest id card) there is activity by the activation zone at (back side of photograph) on applied metal layer.Consequently, tag card is deposited at ambient temperature.Within ten hours, there is no change color.After red background and X start to appear at 11 hours and appear at completely after 16 hours.

Equally, can be produced on top has and only has red background, only has X, and there is the guest id card of " refusal " at " expiring " and " effectively " and back.

In equipment, photograph can be not destroyed, and it can be used for filing.

Example 13: toy, magic and greeting card.

Be similar to the equipment of example 7, but have vocabulary as " happy birthday " with printing, figure is as heart shape diagram, clover, and photo, information and the figure of a large amount of manual drawing design drawings and other types replace bar code and red background.With image, figure and information replace the appearance of bar code.Active equipment cuts into multiple different shape equally, as has heart and the flower shape of red background.They are all from metal to red change color.

Example 14: wrist strap.

100 microns, 1 dust non-metal surfaces of 25 centimetres of x20 centimetre of metallized polyester films is brushed and is had one deck example 3 activating mixtures dry with #30 metal lean.Cut into 25 centimetres x1 centimetre rectangular and folding so that activator coating adhesion is made a wrist strap on metallization face.At room temperature the change color of adhesive surface is in ten hours and unbonded part is still unchanged.

Same, also can manufacture the wrist strap as shown in Figure 13 and 14.

Example 15: the preparation of non-readable (deactivation) RFID inlay machine.

RFID inlay machine/repeater-transmitter [from the Mu-Gahat company of California Sani Wei Er obtain and Figure 37 (a) required] application an activator band having compared with the activator of thick layer and higher concentration.RFID inlay machine antenna make of aluminium thin layer.At room temperature the antenna of this equipment slowly start dissolve.Antenna different breaking-in periods in time, are as shown in Figure 37 (b)-37 (d).Complete RFID inlay machine is presented at the top of every photo.Dissolve in approximately 2 days near the antenna of chip.Etching antenna is made non-can reading chip.

Example 16: etching facial mask.

16-A: there is the facial mask of image with resist (state of Wisconsin Racine company, S.C.Johnson polymkeric substance, acryl resin 77) screen printing on the metal covering of 100 micron metal mylars.This image is transparent and sightless substantially.The activator band of this equipment use-case 5 activates and is placed in the drying box of 55 DEG C.The image of this screen printing occurred in 30 minutes.

The antenna traces of 16-B:RFID inlay machine is on the metal of metallized polyester film, to use printer printing and making.The activator band of use-case 5 is bonded in film on the metallic coating of activator coating covering.Two simple models (leaning to one side) as described in Figure 38 (a).All non-facial mask aluminium has dissolved and has made the antenna as described in Figure 38 (b) two days later.

Similarly antenna traces is picked up and is covered antenna and make by antenna being placed in steam and boiling water with metallized polyester film.

Example 17: time dependent transparency.

The activator band bonding metal mylar of use-case 5.Can use Te Wen-Albert numeral opacimeter, pattern 628 records the transparency of equipment different times at 25 DEG C.Transparence value is as shown in figure 39 to time diagram.From scheming, can find out that almost transparency has not a particle of a variation in 20 hours.While becoming more and more transparent and completely saturating along with this binding appts of time.

Visible transparency is greatly after 27 hours.This result shows that be about 70% the induction period of this equipment.

Example 18: with hot water and vapor etch metallized polyester film.

The 100 micron metal mylars with about 125 dust thickness aluminium laminations are placed on and are equipped with in the conical flask that the 500mL of 100 DEG C of distilled water 200g is clean.Starting irregular dissolving at 10 minutes inner metal layers, is first that boiling/bubbling (may be also due to aerial oxidation to a certain extent) was then dissolved completely in 15 minutes.

The 100 micron metal mylars with about 125 dust thickness aluminium laminations are placed on and metal level are housed on boiling water beaker towards steam.Metal level starts irregular dissolving (in the dissolving slowly of place of volatilization steam condensation) and then dissolved completely at 10 minutes.

Although slow still metal level also can dissolve with steam under vacuum.

As being dissolved in heat or boiling water at the very thin aluminium lamination of mylar last layer, it can be used for monitoring washing and dry project, as vessel and laundry.

Example 19: aluminium foil/controller etching test.

Within 6 hours, then in the pressure cooker of 125 DEG C (20PSI), within 2 hours, process the aluminium foil of 15 micron thick with the steam on boiling water.This aluminium foil is somewhat dimmed a little but not do not dissolve.

Example 20: xeothermic (Control experiment) effect.

100 micron metal polyester films were 180 DEG C of heating 2 hours.Disregard small loss of gloss, there is no variation.

Example 21: the effect of pervious course on moise-heat sterilization indicating equipment.

On 100 micron metal polyester films by polymer solvent coating below 10% and make the dry coating of 8 micron thick on metal covering.Film cutting is slit into the piece 2-30 minute that then sterilizes at 120 DEG C.The needed time of dissolving metal sees the following form shown in (table 2).

Aluminium lamination under some polymkeric substance 8 micron coatings of table 2. dissolves the needed time completely.

Polymkeric substance	Time (dividing)
		Nothing	5
PECH	10
		CAB	15
PolyiBM	15
		CAA	30

PECH: Hydrin, CAB: cellulose acetate butyrate, PolyiBM: poly-n-butyl methacrylate, CAA: Polyvinylchloride-polyvinyl acetate-polyvinyl alcohol copolymer

Example 22: the effect of naturally osmotic layer on perviousness activator

100 micron metal mylars are by polymer solvent coating below 10% and on metal covering, make the dry coating of 8 micron thick.It is then bonding with the activator band of example 5 that film cutting is slit into piece.This activated sample is placed in the drying box of 55 DEG C and needed time to be determined by activator (phosphoric acid).The needed time of dissolving metal sees the following form shown in (table 3).

The aluminium lamination of table 3. different polymkeric substance 8 micron coatings at 55 DEG C dissolves the needed time completely.

Polymkeric substance	Time (dividing)
		Nothing	20
CAB	65
		PVAc	75
PECH	120
		CAA and PolyiBM	About 10 days
Polystyrene and PVC	Even after six months, there is no sign yet

PVAc: polyvinyl acetate, PECH: Hydrin, CAB: cellulose acetate butyrate

Example 23: adjuvant is to molten molecule bronze ink color changeable effect.

Molten point of interest (copper-zinc alloy) ink (PMS871 gold) of joslyn hi-voltage Bu Ladeng Saudi sweet smell is diluted to 50% with dioxolanes.In the golden coating of 2mL dilution, add about 30 kinds of different organic additive 0.25g, be heated to adjuvant and dissolve and use #10 metal lean to brush coating on 100 microns of mylars.Cut into little strip and then at 120 DEG C, use steam treatment 5,10,20,30 and 50 minutes.Adjuvant below almost deepens the effect of brown/black in time to gold plating variable color and gold plating.

Gallic acid

Trimerization glyoxal hydrate

Trihydroxybenzoic acid methyl esters

3,3 ', 4.4 ' benzophenonetetracarboxylic acid

Jia Liyatai propane

Ferric salicylate

Zinc sulphide

Adjuvant below to water-soluble golden coating in the effect aspect gold plating variable color:

Potassium ferrocyanide

The potassium ferricyanide

Test some other activator and there is different chemical functionals and characteristic.Strong acid, solvent and oxygenant, example hydrochloric acid and NaOH, have above-mentioned effect,, at room temperature just starts reaction (start to bubble, extraordinary image produces hydrogen) in admixture/container that is.Some weak acid and solvent, as phosphoric acid and sodium carbonate at room temperature react slow but in mixed number minute, they also start to bubble.But, weak acid relatively, solvent and oxide, as sodium bicarbonate, sodium nitrite, sodium phosphate and sodium acetate, they have corresponding reaction.The lower effect of additive concentration is fewer, and vice versa.

Most of activators are desirable is relatively gentle or weak, and they dissolve or dissolve and approach desirable technique/sterilisation temp.In this way, they can prevent antedating response under condition around.

Example 24: the adjuvant effect in the pervious course on moise-heat sterilization indicating equipment.

100 micron metal mylars are used in the 10% acetylbutyrylcellulose solution coatings that contains 40% (taking solid as main) in tetrahydrofuran and have different chemical functionals and characteristic adjuvant.Strong and warm nature acid, alkali and oxygenant have above-mentioned effect.But, weak acid (carboxyl, phenol and poly alcohol), alkali (amine) and oxygenant have desirable characteristic.Adjuvant below produces effect with the metal level that 120 DEG C of steam treatment are crossed in dissolving.For example, Jia Liyatai propane, benzoic acid, diphenylglycollic acid, iron ammonium oxalate, ferric acetyl acetonade has desirable characteristic, and they dissolve through 30 minutes 120 DEG C of aluminium laminations that steam treatment is crossed.

100 micron metal mylars are printed with " sterilizing " with laser photography machine on non-metal surfaces.The 10% acetylbutyrylcellulose solution coatings that contains about 40% Jia Liyatai propane dry for metal level.Strip is exposed to lower 30 minutes of the steam of 120 DEG C.Appearance that metal level dissolves and vocabulary " is sterilized ".

Example 25: use hydrogen peroxide etching

The molten molecule bronze ink (copper-zinc alloy, PMS871 gold) of joslyn hi-voltage Bu Ladeng Saudi sweet smell is diluted to 50% with dioxolanes.In the coating of 2mL dilution, add different adjuvant 0.25g, heating for dissolving is also used #10 metal lean brush coating on 100 microns of mylars.Cut into little strip and then at 70 DEG C, use hydrogen peroxide steam treatment 4 hours.First sodium dihydrogen phosphate and tetrabutyl ammonium bromide make gold plating variable color then develop into green.

0.5g and 1g tetrabutyl ammonium bromide are dissolved on 5g acryl resin 77 metal covering at metallized polyester film coating then the drying box inner drying of 70 DEG C 5 minutes.The coating of sheet is exposed to the hydrogen peroxide water vapour 4 hours of 70 DEG C.Metallic coating dissolves and this film becomes clean.

Example 26: for the metallic particles indicator of moise-heat sterilization

250g bonding agent (the fragrant metal ink adjuvant in Bu Ladeng Saudi, product #9w3021N) and 400g sodium acetate solution (40g is dissolved in 360g water) are housed in the plastic containers of 1L mixes under moderate agitation.In the plastic containers of 2L, pack 500g metal ink indicator [the fragrant aluminium ink in Bu Ladeng Saudi (being called silver-colored ink), production code member 9W2967J] and above-mentioned sodium acetate mixed solution into mixes under fully stirring.#10 metal lean brush coating on 50 microns of mylars for consequent metal ink.This coating is dried 10 minutes in the drying box of 70 DEG C.

Film [Figure 40 (a)] to sheet carries out the processing of different condition, as at 160 DEG C xeothermic 30 minutes [Figure 40 (b)], steam 30 minutes at 100 DEG C, 50 DEG C of saturated moist next weeks [Figure 40 (c)], 100% ethylene oxide gas two hours under hydrogen peroxide steam one hour and room temperature at 60 DEG C.It is transparent that coating does not become under these conditions.Coating becomes transparent and is printed on information below and color becomes as seen with processing 30 minutes under 120 DEG C of steam, as shown in Figure 40 (d).

Example 27: removable boundary line moise-heat sterilization indicating equipment

On the metal covering of 100 micron metal mylars with commercially available polyurethane latex (#8294, transparent gloss, aqueous polyurethane, general application, Ritchie Wood, New Jersey) be coated with the rectangular of one deck 0-10 mil wedge shape 10 centimeter length and be dried 15 minutes at 70 DEG C.Obtain polyurethane wedge shape coating.

40g is housed in the plastic containers of 1L and is dissolved in the sodium acetate in 250g acryl resin 77.This potpourri coating at 70 DEG C dry 15 minutes in polyurethane wedge shape coating.

Cut into little strip, be arranged on green paper also with 120 DEG C of time cycles that steam treatment is different.At 120 DEG C, directly sheet [Figure 41 (a)], with steam treatment 15 minutes [Figure 41 (b)], 21 minutes [Figure 41 (c)], 30 minutes [Figure 41 (d)], and 45 minutes [Figure 41 (e)] as shown in figure 41.Comprise that sample takes out from sterilizer above-mentioned T.T., check and processing procedure again.

Such equipment provides a manufacture for the integrated of steam and other sanitizer or has substantially changed, level 1-6 or level 1, the chance of 3-6 (may entirely have more senior) type indicator, adopt and be applicable to metal, metal thickness, material and thickness carry out the precursor for wedge shaped layer and activator or indicator.

Example 28: metallic particles is that indicator and tetrabutyl ammonium bromide are hydrogen peroxide activator precursor and plasma thereof.

The tetrabutyl phosphonium bromide aqueous ammonium of 50g metal ink indicator (the fragrant silver/aluminium ink in Bu Ladeng Saudi, production code member 9W2967J) and 20g50% is housed in plastic containers and mixes.#10 metal lean brush coating on 50 microns of mylars for consequent metal ink.This coating is dried 15 minutes in the drying box of 70 DEG C.

Film [Figure 42 (a)] to sheet carries out the processing of different condition, as at 160 DEG C xeothermic 30 minutes [Figure 42 (b)], 60 DEG C of saturated humidities next day [Figure 42 (c)], steam 30 minutes [Figure 42 (e)] at steam 30 minutes [Figure 42 (d)] and 120 DEG C at 100 DEG C.It is transparent that coating does not become under these conditions.Coating starts bleach and exceedes 6 hours when being exposed in the hydrogen peroxide steam of 60 DEG C, as shown in Figure 42 (f).

Example 29: metallic particles is that indicator and sodium thiocyanate are the precursor of oxirane disinfection indicator

The sodium thiocyanate water solution of 50g metal ink indicator (the fragrant silver/aluminium ink in Bu Ladeng Saudi, production code member 9W2967J) and 20g50% is housed in plastic containers and mixes.#10 metal lean brush coating on 50 microns of mylars for consequent metal ink.This coating is dried 15 minutes in the drying box of 70 DEG C.

Film [Figure 43 (a)] to sheet carries out the processing of different condition, as at 160 DEG C xeothermic 30 minutes [Figure 43 (b)], 60 DEG C of saturated humidities next day [Figure 43 (c)], steam 30 minutes [Figure 43 (d)] at 100 DEG C, hydrogen peroxide steam 6 hours [Figure 43 (f)] at steam 30 minutes [Figure 43 (e)] and 60 DEG C at 120 DEG C.It is transparent that coating does not become under these conditions.Coating starts bleach and exceedes 6 hours when being exposed in the moist oxirane of 60 DEG C, as shown in Figure 43 (g).

The instruction thin metal layer of same example 28 and 29 and their particle can be used for the monitoring of chemicals.

Selectivity described in consequent routine 26-29 and the certainly property read sterilization indicators can be developed for present invention.

Example 30: halogen compounds is as precursor and bonding agent.

In with magnetic stirrer 500mL wide-necked bottle, add 200g tetrahydrofuran and 50g fire retardant-700 (Dover chemical industry, Dover, Ohio) to add 50g polyvinylidene chloride-acrylonitrile copolymer in appropriateness stirs.Agitating solution makes bonding agent dissolve for 1 hour.On the metallized polyester film with 50 dust aluminium laminations, be coated with the rectangular of one deck 5 mils and be dried 5 minutes at 50 DEG C with this solution.This coating adhesion is on the polyethylene film of 1 mil.This its coating of bonding sample to sun exposed in the sun.Metal level dissolves after about 2 hours and prints the red paper that has " radiation " to be placed under metallic film and occurs.

With polyvinyl acetate as bonding agent, trichloroethanes, trichloroacetamide and ethyl trichloroacetate equally also can be prepared as the similar devices of precursor (part dry).

Example 31: without the oligomeric halogen compounds of thickness of bonding agent

Several about 50 microns by fire retardant (as fire retardant 700), machine oil (as machine oil 121) and incombustible agent incombustible agent 991) (by Dover chemistry, Dover, Ohio, provides) layer makes by coating on the mylar that has 50 dusts and print " radiation " aluminium lamination on polyester.These equipment and 25 microns of mylars are bonding to prevent in radiation and to be exposed to the hydrogen chloride leakage producing under 500000 rads of about 100 kiloelectron-volts of X ray.Metal level dissolves and information " radiation " becomes visible.

Example 32: radiation indicating equipment.

In the time that the potpourri of bronze (as the bronze of copper and zinc) fine grained and halogenated alkane (as many not fire retardants 700 of chemistry) is used ion irradiation radiation, as ultraviolet/sunshine, golden particle becomes redness.Same aluminium fine grained under above-mentioned radiation dissolves.Therefore, the potpourri of halogen compounds and metal can be used for the indicator as radiation dose.

Example 33: definite method of activator concentration.

There are 125 dust aluminium laminations and having thereafter on the metallized polyester film of red paper, drip the phosphoric acid solution of a droplet variable concentrations (5-85%) to the diverse location of metal level, then record hot coloured paper Zhang Ganggang and start to occur (working as a very thin layer, while thering is no etching as remaining 10-20 dust) and the complete time of (metallization is dissolving completely substantially) as seen.These data are depicted as Figure 44.

Should be noted that difference between the first sign of bleach and complete transparent increase is the reduction of concentration.This means, adopt different activator (or its precursor) concentration, definite division of induction period and end point is different.

Same same time interval can be determined by 0.05% recruitment of 50% phosphoric acid solution.The method of this definite chemicals/activator concentration is very sensitive, can determining by 0.05% concentration.

Also be confirmed as 0.05% solution increasing of 50% phosphoric acid.The method of this definite a kind of chemicals/activator concentration is very sensitive, can determine by+0.05% concentration.

Similarly experiment is also carried out on the metal plastic film that scribbles osmotic polymer.

The method also can be used to Yu Qi or the activator of steam phase or the concentration of its precursor and determines.

Easily make malicious chemical assay in concentrated activator or they at gas or vapor phase.

Can be by thering is or not have rectangular of the metal plastic film of permeation coating, be immersed in solution be exposed to steam or gas in determine the concentration of activator.

Example 34: for monitoring the equipment of radon and α particle.

One for monitoring the equipment that automatically performs/measure of α particle and alpha activity element, as the radon of creation when cellulose nitrate thin layer (15 microns) being carried out to etching with potassium hydroxide on metallization PET.These equipment are except the metal level with thin replaces coloring agent/indicator layer, and it is disclosed that other are similar to U.S. Patent number 4788432 (being incorporated by reference) herein.

25g cellulose nitrate (12% nitrogen) powder containing 30% alcohol under agitation joins 125g ethyl acetate, and 5g butanols, in the potpourri of 8g ethylene glycol monoethyl ether and 4g dioctyl phthalate.4% cellulose nitrate cellulose solution is by obtaining by 100mL ethyl acetate dilution 40g cellulose nitrate stoste.

With the thin film cladding device of 0.003 inch on the 100 micron metal mylars with about 100 dust aluminium laminations by above-mentioned cellulose nitrate dilute solution coating.This coating is dry in the drying box of 70 DEG C.

Use this film of α-particleirradiation coming from source, polonium-210 to be then placed on red paper.The potassium hydroxide solution of 6 moles drips for the etched emissivity film of the recessive vestige of selectivity.

Micro-speckle (red color, because red paper) started to occur after about three hours.Along with time spot becomes large.Spot because of the recessive vestige that produces by α particle with potassium hydroxide selectively, etching fast and producing.Potassium hydroxide equally also carries out etching and occurs punctation the thin metal layer under recessive vestige.

Raw material (except coloring agent) and method are disclosed in U.S. Patent number 4788432, also can be by reference for equipment disclosed herein and that mentioned here.

The sensitivity of radon monitoring equipment can by equipment (metal plastic film has the shallow layer of recessive vestige that one deck is produced as cellulose nitrate by material) place layer of active carbon and improve, radiomaterial can be absorbed by activated charcoal and in the time radiating α particle, will on cellulose nitrate layer, produce recessive vestige as radon and product thereof (comprise by neutron-alpha reaction and producing).

Claims

1. an indication mechanism, it comprises:

Substrate has metal indicator layer on described substrate;

Activator or its precursor layer, wherein, in the time contacting or be placed in reagent to be monitored or process, described activator or its precursor layer and described indicator react; And

Be positioned at the information on described substrate, wherein said information only at described activator or its precursor layer with described indicator reacts and will be visible after described indicator destruction.

2. indication mechanism claimed in claim 1, wherein said indicator layer comprises such material: described material has at least one performance in the electric conductivity of being selected from, reflectivity, height opacity, autohension and impenetrability, and after contacting with described activator, described material can etched or destruction.

3. indication mechanism claimed in claim 1, after wherein said indicator layer contacts with described activator, its reaction product has at least one performance being selected from non-conductive, nonreflective, perviousness and the transparency or translucence.

4. indication mechanism claimed in claim 1, wherein said metal indicator comprises metal, metal alloy, semi-metallic or semiconductor material.

5. indication mechanism claimed in claim 4, wherein said metal or metal alloy is selected from the metal, copper and the alloy that react with activator.

6. indication mechanism claimed in claim 4, wherein said metal or metal alloy is selected from alkaline metal, earth alkali metal, transition metal, late transition metal, group of the lanthanides and actinide metals and their alloy.

7. indication mechanism claimed in claim 6, wherein said metal is selected from aluminium, tin, zinc, copper, manganese, magnesium, nickel, cobalt, iron, sodium, potassium, lithium, calcium, gallium, caesium, germanium, indium, silver and their alloy.

8. indication mechanism claimed in claim 7, wherein said metal is aluminium, copper, zinc or tin.

9. indication mechanism claimed in claim 4, wherein said metal and metal alloy comprise the alloy reacting with water, acid, alkali, chemicals, chemistry or biopreparate and salt.

10. indication mechanism claimed in claim 6, the alloy that wherein said metal alloy comprises aluminium, copper, tin or zinc.

11. indication mechanisms claimed in claim 4, wherein said alloy comprises at least one metal.

12. indication mechanisms claimed in claim 1, thus wherein said activator comprises and the react composition of the chemical composition generation irreversible change that causes this indicator of described indicator.

Indication mechanism described in 13. claims 12, wherein said activator comprises at least one reagent being selected from water, oxygen or organic or inorganic acid, alkali, salt, chemistry or biopreparate or chelate.

14. indication mechanisms claimed in claim 1, wherein said activator precursor layer comprises the precursor of described activator.

Indication mechanism described in 15. claims 13, wherein said activator is mineral acid.

Indication mechanism described in 16. claims 15, wherein said activator is selected from phosphoric acid, phosphorous acid, hydrochloric acid, nitric acid, sulfuric acid, sulfonic acid or their potpourri.

Indication mechanism described in 17. claims 12, wherein said activator is: oxyhydroxide, alkoxide or the aromatic oxide of metal; Or cationic oxyhydroxide, alkoxide or the aromatic oxide of nitrogen.

Indication mechanism described in 18. claims 12, wherein said activator is the combination of weak acid strong alkali salt, strong acid weak base salt, strong acid and strong base salt or weak acid and weak base salt.

Indication mechanism described in 19. claims 12, wherein said activator is cationic halogenide, oxide, nitrate, nitrite, phosphate, phosphite, phosphonate, silicate, sulfate, hydrosulfate, sulphite, sulfide, disulfide, sulfonate, cyanate, prussiate, thiocyanate, acetylacetonate, carboxylate, percarboxylic acids salt, carbonate or the supercarbonate monovalence, divalence or Tricationic or nitrogen, sulphur, phosphorus, halogen of metal, or their potpourri.

Indication mechanism described in 20. claims 19, wherein said activator is ammonium bromide, ammonium thiocyanate, lime chloride, cupric chloride, cupric ammine complex, diacetone lithium, lithium chloride, lithium formate, phosphorus, phosphorus pentoxide, potassium acetate, Potassium Benzoate, potassium bromide, potassium chloride, potassium ferrocyanide, the potassium ferricyanide, potassium formate, sodium acetate, sodium bicarbonate, sodium bromide, sodium carbonate, Zassol, sodium diethyldithiocarbamate, sodium iodide, sodium metasilicate, sodium nitrate, sodium sulphite, sodium tetrafluoroborate, sodium tetraborate, sodium thiocyanate, sodium thiosulfate, tetraethylammonium bromide, zinc chloride or their potpourri.

Indication mechanism described in 21. claims 12, the chelate that wherein said activator is metal cation or complex compound.

Indication mechanism described in 22. claims 21, wherein said activator is the complex compound of metal cation and amine or ammonia.

Indication mechanism described in 23. claims 22, wherein said activator is the complex compound of cupric chloride or nickel chloride and amine or ammonia.

24. indication mechanisms claimed in claim 1, it comprises: with the precursor of described metal indicator layer close contact or the described activator in described activator precursor layer that is close.

Indication mechanism described in 25. claims 24, wherein said activator is oxygen, chemical gaseous thing or water.

Indication mechanism described in 26. claims 12, wherein said activator is moisture, steam or microwave, and wherein said activator or its precursor directly react with described metal indicator layer, and does not need directly to contact with this metal indicator layer.

Indication mechanism described in 27. claims 26, wherein said metal indicator layer is together with base plate bonding, to form types of metallized plastic films.

28. indication mechanisms claimed in claim 1, wherein said activator or precursor layer are until while being exposed in reagent to be detected or process, just can react with described indicator.

Indication mechanism described in 29. claims 28, wherein said reagent is moisture, steam, oxirane, formaldehyde, ozone, Peracetic acid, hydrogen peroxide, chemicals or biopreparate.

30. indication mechanisms claimed in claim 1, wherein said indicator layer is arranged on substrate.

Indication mechanism described in 31. claims 30, wherein said substrate is less than the plastic sheeting of the continuous metal layer of approximately 10,000 dusts for having thickness.

Indication mechanism described in 32. claims 31, wherein said indicator layer is the continuous metal layer that thickness is less than approximately 1,000 dust.

Indication mechanism described in 33. claims 30, wherein said indicator layer is the stratum granulosum that thickness is less than approximately 10 microns.

34. indication mechanisms claimed in claim 1, it comprises; For the bonding agent of described activator; And the bonding agent that described active agent layer and indicator layer are bonded together.

Indication mechanism described in 35. claims 34, wherein said indicator layer is attached on substrate.

Indication mechanism described in 36. claims 35, wherein said substrate is the plastic sheeting with contact adhesive.

37. indication mechanisms claimed in claim 1, it comprises: for the bonding agent of described activator.

Indication mechanism described in 38. claims 37, wherein said indicator layer is attached on substrate.

Indication mechanism described in 39. claims 38, wherein said substrate is the plastic sheeting with contact adhesive.

40. indication mechanisms claimed in claim 1,

Activator or its precursor in wherein said activator or its precursor layer dissolve or are scattered at least one hypothallus.

41. 1 kinds of indication mechanisms, it comprises the indicator strip that is bonded together with at least one bonding coat and the compound of activator band, wherein said indicator strip comprises the substrate adhering to mutually with at least one metal level; Described activator band or the band that comprises the precursor that can produce activator are made up of the substrate adhering to mutually with at least one hypothallus, and wherein said hypothallus contains activator or its precursor.

42. indication mechanisms claimed in claim 1, it can be used in monitoring material or process.

Indication mechanism described in 43. claims 42, wherein said material is chemicals, chemicals or biopreparate.

Indication mechanism described in 44. claims 42, wherein said process be time, temperature, Time-temperature, freezing, thaw, the degree of boiling, microwave, pressure, radiation and the sterilization of heating, cooling, humidity, food, wherein said sterilization comprises with steam, oxirane, hydrogen peroxide, hydrogen peroxide plasma, formaldehyde, the sterilization that xeothermic or ionising radiation is carried out.

Indication mechanism described in 45. claims 44, wherein said Time-temperature process is shelf-life for monitoring perishables, availability, freshness, and that wherein said perishables comprises is fresh, refrigeration or freezing vegetables, fruit, meat, fish, poultry, dairy products, baked product, fruit juice, one or more in medicine, vaccine, biological sample, cosmetics, reactive compounds, biogenetic products, battery, x-ray film or the sensitive film of food, soft drink, alcoholic beverage and the non-food stuff class of the cooking in advance.

Indication mechanism described in 46. claims 45, wherein said biological sample is serum, blood or blood plasma.

Indication mechanism described in 47. claims 41, it also comprises described indication mechanism is bonded in to the adhesive phase on to be monitored.

Indication mechanism described in 48. claims 41; it comprise there is thin metal layer, patterned layer that barrier material is made and the substrate of active agent layer; wherein after described indication mechanism is activated; described barrier material is protected the selected specific region of described pattern on described indicator strip, thereby makes all the other regions of metal level form information or form at least one conductive path or formation metal pattern for electronic equipment.

Indication mechanism described in 49. claims 48, it also comprises electronic chip or element that at least one is connected with described conductive path.

Indication mechanism described in 50. claims 12, wherein active agent layer is to be placed at least a portion of at least one conductive path of the electronic equipment being made up of at least one electronic chip, wherein said activator can destroy described conductive path.

Indication mechanism described in 51. claims 50, wherein said electronic equipment is RFID equipment or EAS equipment.

52. indication mechanisms claimed in claim 1, wherein, described information is positioned at least one side of described indicator layer, and wherein said information comprises color, word or mark.

Indication mechanism described in 53. claims 52, wherein said information is to show on the both sides of described indicator layer.

Indication mechanism described in 54. claims 53, it comprises at least two kinds of information, and these two kinds of information start to show when different.

Indication mechanism described in 55. claims 54, wherein when the described indication mechanism of application is processed in a project or before, state or the quality of the project described in the first demonstration information instruction, and after processing described project, state or the quality of the project of the second demonstration information individually or described in indicating together with described the first demonstration information.

Indication mechanism described in 56. claims 55, wherein said the first demonstration information instruction be the degree of not boiling, freshness, availability, acceptability of project, undressed, unexposed or not sterilization, unavailability, inadmissibility; And described the second demonstration information individually or indicate together with described the first demonstration information described project after treatment degree of boiling, expire, go bad, unavailability, inadmissibility, treated, through that expose, aseptic, availability and acceptability.

57. indication mechanisms claimed in claim 1, wherein, the metal indicator that described metal indicator layer comprises particle form.

Indication mechanism described in 58. claims 57, the activator in wherein said indicator and described activator or its precursor layer or its precursor include instruction ink, pigment, gel and plastisol.

Indication mechanism described in 59. claims 58, wherein said indication mechanism contains liquid media.

Indication mechanism described in 60. claims 14, the described precursor of wherein said activator is acid, alkali, salt, organometallics or reagent.

Indication mechanism described in 61. claims 60, wherein said precursor is phosphorus pentoxide.

Indication mechanism described in 62. claims 14, it comprises a kind of precursor of described precursor.

Indication mechanism described in 63. claims 62, the precursor of wherein said precursor is white phosphorus or yellow phosphorus.

Indication mechanism described in 64. claims 14, wherein said precursor halides that be monomer or polymerization, halogenide, halogen compound, sulfonium compound or phosphorus compound.

65. indication mechanisms claimed in claim 1, it also comprises: wherein increased the system of one or more extra plays, wherein said extra play is selected from adhesive phase; Permeable enter the layer of activator; Permeable enter the wedge shaped layer of activator; The layer of isolation activator; Reactive, destructible or degradable separation layer; Stop marker; Amendment marker; Activate marker; Information or image formation layer, separating layer, can remove layer, self-assembling formation oxide skin(coating); Stealthy layer; Can active coating; Microcapsule layer; Or can thermal printing layer.

Indication mechanism described in 66. claims 40, it comprises band.

Indication mechanism described in 67. claims 66, it comprises band, described band has two Tape dispenserses that are used to indicate agent band and activator band, and wherein, in the time that described band is applied on container, described indicator band and activator band are distributed simultaneously.

68. indication mechanisms claimed in claim 1 have wherein been printed information by thermal printing on described substrate.

Indication mechanism described in 69. claims 68, wherein said thermal printing is direct thermal printing.

70. indication mechanisms claimed in claim 1, wherein said indicator layer or described system activation evergy required time that changes is that the one or more parameters that are selected from following group by change change or adjust: the thickness of described active agent layer; The thickness of described indicator layer; The thickness of permeable layer; The concentration of described activator; The concentration of described precursor; The concentration of adjuvant in described activator; The concentration of adjuvant in described permeable layer; The character of solvent, surfactant and catalyzer; The character of described active agent layer; The character of described indicator layer; The character of described permeable layer; The character of additive layer; And the character of catalysts and retarding agent.

71. indication mechanisms claimed in claim 1, optical waveguide monitor, electronic circuit or EAS that wherein this system is pinpoint accuracy.

72. indication mechanisms claimed in claim 1, wherein this system is following form: safety label; The retail label of self-timing; Biological industry operation watch-dog; Prevent reusable self termination label; Safe ID label; Visitor's label; Parking self termination label; Packaging and shipping label; Wrist strap; For the time explanation ticket of train, motorbus, site activity, theater; The self termination pass in sightseeing, emergency ward, hospital, museum and other places; The runway pass; For showing the checked safety label of luggage, wallet, case and bag after the scanning of airport; With the self termination visitor label sending with electronic type at unattended but by visitor's entrance of video management.

73. indication mechanisms claimed in claim 1, wherein this system is following form: toy, novelty, information, pattern, pattern, Gift Card or greeting card.

Monitor the method for the state of medical product, food or biological waste for 74. 1 kinds, it comprises: indication mechanism claimed in claim 1 is placed in the external packing of described medical product, food or biological waste.

Whether 75. 1 kinds of monitorings there is the method for toxic chemical, reagent or water, and it comprises: indication mechanism claimed in claim 1 is placed in to region to be monitored, and from this indication mechanism obtaining information.

Monitor the method for the state of perishable commodities for 76. 1 kinds, it comprises: indication mechanism claimed in claim 1 is placed on described perishable commodities or near it, and wherein said perishable commodities are food or non-food.

The method that the time limit consumer of 77. 1 kinds of monitoring articles uses, wherein said article be open or in use, and described article should use within a certain period of time, described method comprises: indication mechanism claimed in claim 1 is placed in near of monitored article, wherein said article are selected from: beverage, food, health products, individual or residential care product.

Prepare the method for the indication mechanism described in claim 41 for 78. 1 kinds, it comprises: activator belt is pressed onto on indicator strip, and wherein said indicator strip is metal indicator band.

Prepare the method for indication mechanism claimed in claim 1 for 79. 1 kinds, it comprises: on metal indicator, apply active agent layer, wherein this indication mechanism has or do not have: permeable layer; Permeable wedge shaped layer; Separation layer; Reactive, destructible or degradable separation layer; Stop marker; Amendment marker; Activate marker; Information or image formation layer, separating layer, can remove layer, self-assembling formation oxide skin(coating); Stealthy layer; Can active coating; Microcapsule layer; Or can thermal printing layer.

The method of preparing indication mechanism described in 80. claims 79, it also comprises: apply extra play.

81. indication mechanisms claimed in claim 1, wherein this system is a part for RFID, EAS or printed circuit board (PCB).

82. indication mechanisms claimed in claim 1, its detection for the monitoring of chemicals, biochemical reagents or biological reagent and quantitative measurement, this indication mechanism comprises: for monitoring the metal of chemicals, biochemical reagents or biological reagent, and described monitoring is based on etching metal or Metallic Optical Waveguide pipe.

Indication mechanism described in 83. claims 43, wherein said chemical reagent is lethal agent, cause blister agent, affect preparation, never poison, lung's reagent, anergy reagent or the riot control agent of blood.

Indication mechanism shown in 84. claims 83, wherein said chemical reagent is selected from: cyanogen chloride, hydrogen cyanide, ethyl dichloroarsine, methyl dichloroarsine, phenyldichloroarsine, Lewisite, 1,5-Dichloroethyl thioether, two (the 2-chloroethyl sulfenyl) ethane of 1,2-, two (the 2-chloroethyl sulfenyl) n-propanes of 1,3-, Isosorbide-5-Nitrae-bis-(2-chloroethyl sulfenyl) normal butane, two (the 2-chloroethyl sulfenyl) n-pentanes of 1,5-, 2-chloroethyl chloromethyl thioether, two (2-chloroethyl) thioether, two (2-chloroethyl sulfenyl) methane, two (2-chloroethyl sulfidomethyl) ether, two (2-chloroethyl sulfidomethyl) ether, two (2-chloroethyl) ethamine, two (2-chloroethyl) methylamine, three (2-chloroethyl) amine, tabun, cerin(e) sarin, soman, cyclosarin, GV, VE, VG, VM, VR, VX chlorine, chloropicrin, phosgene, two phosphorus alkene, (BZ) 15 doses, EA3167 agent, kolokol-1, capsicum water spray, CS gas, CN gas or CR gas.

Indication mechanism described in 85. claims 43, wherein said chemicals is poisonous industrial chemical.

Indication mechanism shown in 86. claims 85, wherein said poisonous industrial chemical is acetone cyanohydrin, acryl aldehyde, vinyl cyanide, vinylcarbinol, allylamine, allyl chlorocarbonate, allyl isothiocyanate, ammonia, arsenic trichloride, arsine, Boron tribromide, boron chloride, boron trifluoride, bromine, bromine chloride, BPF, bromine trifluoride, carbon disulphide, carbon monoxide, carbonyl fluoride, carbonyl sulfide, chlorine, chlorine pentafluoride, chlorine trifluoride, chloroacetaldehyde, chloro-acetone, chloroacetonitrile, chloracetyl chloride, chlorosulfonic acid, crotonaldehyde, cyanogen, 1,2-dimethyl callosity, diborane, ketene dimer, dimethyl suflfate, diphenyl-methane-4,4 '-diisocyanate, ethyl chloroformate, thio-ethyl chloride, ethyl dichloride D2EHDTPA, the sub-phosphoryl chloride phosphorus oxychloride of ethyl, dibromoethane, aziridine, oxirane, fluorine, formaldehyde, hexachlorocyclopentadiene, hydrogen bromide, hydrogen chloride, hydrogen cyanide, hydrogen fluoride, hydrogen iodide, hydrogen selenide, sulfuretted hydrogen, iron pentacarbonyl, isobutyl chlorocarbonate, isopropyl chlorocarbonate, isopropyl isocyanate, methylsufonyl chloride, methyl bromide, methylchloroformate, methyl chlorosilane, methyl hydrazine, methyl isocyanate, methyl mercaptan, butyl chloroformate, n-butyl isocyanate, nitric acid, flue gas, nitrogen monoxide, nitrogen dioxide, chloro-carbonic acid n-propyl, parathion, perchlormethyl, phosgene, hydrogen phosphide, phosphorous oxychloride, phosphorus pentafluoride, phosphorus trichloride, sec-butyl chloroformate, seienium hexafluoride, silicon tetrafluoride, antimonous hydride, sulphuric dioxide, sulfuric anhydride, sulfuric acid, chlorosulfuric acid, vikane, tellurium hexafluoride, tert-butyl group isocyanates, tert octyl mercaptan, lead tetraethyl, tetraethyl pyrophosphate, tetramethyl lead, titanium tetrachloride, toluene 2,4-diisocyanate, toluene 2,6 diisocyanate, trichloro-acetic chloride, trifluoro-acetyl chloride or tungsten hexafluoride.

87. indication mechanisms claimed in claim 1, wherein this system is the equipment of monitoring radon and α particle.

Indication mechanism described in 88. claims 30 wherein all comprises indicator layer on the both sides of described substrate.

89. indication mechanisms claimed in claim 1, wherein said active agent layer is positioned on substrate.

Indication mechanism described in 90. claims 89 wherein all has active agent layer on the both sides of described substrate.

91. indication mechanisms claimed in claim 1, wherein said indication mechanism is the equipment that is used to indicate different sterilizing ranks.

The method of 92. 1 kinds of definite reagent concentrations, it comprises: monitor the described indicator layer of indication mechanism claimed in claim 1 being dissolved or being partly dissolved the required time.

The method of 93. 1 kinds of definite reagent concentrations, it comprises: monitor the variation that the described indicator layer of indication mechanism claimed in claim 1 occurs aspect electric conductivity or opacity.